CN102899900B - Emulsion type sizing agent for carbon fiber as well as preparation method and application of emulsion type sizing agent - Google Patents
Emulsion type sizing agent for carbon fiber as well as preparation method and application of emulsion type sizing agent Download PDFInfo
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Abstract
The invention discloses an emulsion type sizing agent for a carbon fiber as well as a preparation method and application of the emulsion type sizing agent. The sizing agent contains 2-40 percent of epoxy resin, 0-97 percent of water, 0.5-14 percent of surfactant, 0.3-12.5 percent of cardanol, 0.1-1.5 percent of formaldehyde and 0.1-2.0 percent of inorganic ammonium salts. The emulsion type sizing agent contains the cardanol and the formaldehyde as toughening and modifying agents, so that when the carbon fiber sized by using the emulsion type sizing agent for the carbon fiber is compounded with an epoxide resin matrix taking polyamine as a curing agent to form a composite material, the interlaminar shear strength is improved by over 30 percent and the carbon fiber composite material is enabled to have higher integral performance. The emulsion type sizing agent contains the inorganic ammonium salts, so that the storage stability of the sizing agent is greatly improved and the phenomena of demixing and non-uniformity of concentration are avoided. According to the emulsion type sizing agent disclosed by the invention, the phenomena of demixing and emulsion breaking in the use process of the sizing agent are avoided. After the carbon fiber sized by the sizing agent disclosed by the invention is stored at normal temperature for five years, the mass percentage of the sizing agent on the surface of the carbon fiber is unchanged.
Description
Technical field
The invention belongs to carbon fiber production field, be specifically related to sizing agent and its preparation method and application for a kind of emulsion type carbon fiber.
Background technology
In carbon fibre reinforced composite, for using sizing agent as transition zone between the carbon fiber that strengthens and matrix resin, sizing agent can connect carbon fiber well, can connect well matrix resin again, make carbon fibre reinforced composite become as a whole, there is very strong overall performance.
Patent CN1318686C discloses a kind of carbon fiber sizing agent, this carbon fiber contains with sizing agent, (A) in molecule, at least there is the compound of an epoxy radicals, (B) have and using ammonium ion as the anionic surfactant to ion, (C) nonionic surface active agent.
But, apply the composite that the carbon fiber after above-mentioned carbon fiber sizing agent starching is made, due to the effect of enbrittling after epoxy resin cure contained in the sizing agent as transition articulamentum, affected effective combination of carbon fiber and matrix resin, made carbon fiber ring epoxy resin-based composite interlaminar shear strength is less, and the overall performance of carbon fibre composite has been caused to great adverse effect.And, storage and the stability in use of above-mentioned carbon fiber sizing agent are poor, in storage and use procedure, there will be creaming of emulsion, emulsion concentration skewness, there are even too early breakdown of emulsion, flocculation, reunion etc., there is the phenomenons such as layering, sinking, muddiness in sizing agent, cannot carry out carbon fiber starching, and can not stir comparatively fast in use and course of conveying, this produces and has brought great inconvenience carbon fiber, and the overall performance of carbon fiber and composite thereof is also brought to very large adverse effect.
Summary of the invention
The shortcoming and deficiency that in order to overcome existing carbon fiber, with sizing agent, exist, primary and foremost purpose of the present invention is to provide a kind of emulsion type carbon fiber sizing agent through toughening modifying, carbon fiber through this sizing agent starching, after making carbon fiber ring epoxy resin-based composite, the sizing agent layer that plays interface connection function between carbon fiber and matrix resin has extremely strong toughness, thereby interface binding power and the interface binding power between sizing agent and matrix resin between carbon fiber and sizing agent are all strengthened greatly, carbon fiber is combined with matrix resin effectively by sizing agent transition articulamentum, formed an organic whole, greatly improved the interlaminar shear strength of carbon fibre composite.And, sizing agent provided by the invention also possesses storage and the good characteristic of stability in use, in storage and use procedure, there will not be creaming of emulsion, emulsion concentration skewness phenomenon, and can stir comparatively fast in use and course of conveying, the performance of having guaranteed sizing agent does not change in storage and use procedure, has greatly guaranteed that carbon fiber and composite thereof have higher overall performance.Guaranteed that carbon fibre composite has higher overall performance.
Another object of the present invention is to provide the preparation method of above-mentioned emulsion type carbon fiber with sizing agent.
A further object of the present invention is to provide the purposes of above-mentioned emulsion type carbon fiber with sizing agent.
Object of the present invention is achieved through the following technical solutions:
An emulsion type carbon fiber sizing agent, the composition that contains following mass percent:
Epoxy resin: 2-40%
Water: 0-97%
Surfactant: 0.5-14%
Anacardol: 0.3-12.5%
Formaldehyde: 0.1-1.5%
Inorganic ammonium salt: 0.1-2.0%.
Described epoxy resin refers to the compound that contains at least one epoxy radicals in molecule, preferably a kind of in bisphenol A type epoxy resin, bisphenol f type epoxy resin or novolac epoxy resin.
The preferred deionized water of described water.
Surfactant is the effect of playing emulsification, and described surfactant is anion surfactant and/or non-ionic surface active agent;
Described anion surfactant is organic ammonium (ammonia) salt and/or aminated compounds, and it contains suc as formula 1, the hydrophobic grouping shown in formula 2, formula 3 or formula 4:
Formula 1
Formula 2
Formula 3
Formula 4
In formula 1-4, R
1, R
2, R
3chain alkyl for hydrogen atom or C1-C3; R
4for divalent aliphatic alkyl; M is the integer of 1-3.
Described non-ionic surface active agent is that the polyalkylene oxide Addition on ethylene thing of senior alcohol ether type is, the polyalkylene oxide Addition on ethylene thing of the polyalkylene oxide Addition on ethylene thing of higher fatty acids type, alkyl phenyl ether type or PO/EO block type polyethers; The preferred polyethylene oxide alkyl ethers of described non-ionic surface active agent, polyethylene glycol oxide alkyl phenylate, polyoxyethylene fatty acid esters, polyethylene glycol oxide aliphatic acid amino ethers, polyol fatty acid ester, polyethylene glycol oxide polyol fatty acid ester, sucrose fatty ester, alkylolamides or polyoxygenated alkyl block virtue polymers.
Described anacardol be between position on be connected with single phenol of C15 unsaturated terminal chain and the mixture of bis-phenol.
Described inorganic ammonium salt is ammonium chloride, ammonium sulfate or ammonium nitrate; This wherein, the stablizing effect of ammonium chloride is best, the therefore described preferred ammonium chloride of inorganic ammonium salt, this is because the hydrogen bond action between ammonium chloride molecule and epoxy resin molecule and hydrone, ionic bond effect are stronger, is conducive to the two also stable existences that combine.
The preparation method of sizing agent for above-mentioned emulsion type carbon fiber, comprises the following steps:
Surfactant is soluble in water, then add epoxy resin, anacardol, formaldehyde, under 500-1000r/min, stir 60-100min; Then at 5000-10000r/min down cut emulsification 15-35min; Finally add inorganic ammonium salt, under 500-1000r/min, stir 15-25min, obtain emulsion type carbon fiber sizing agent;
Described stirring is all to carry out at 40-80 ℃.
Above-mentioned emulsion type carbon fiber can be used in epoxy resin base carbon fiber composite material with sizing agent, as transition zone, connects carbon fiber and epoxy resin-base.
A carbon fiber, contains above-mentioned emulsion type carbon fiber sizing agent, and emulsion type carbon fiber is the 0.1-5% of carbon fiber quality by the quality of sizing agent.
An epoxy resin base carbon fiber composite material, contains above-mentioned carbon fiber, and epoxy resin-base is used polyamine as curing agent;
Described polyamine is the product of hydrogen atom after being replaced by alkyl in amino molecule, and in molecule, contains two or more amino, as ethylenediamine, hexamethylene diamine, diethylenetriamine, m-phenylene diamine (MPD), triethylene tetramine, diaminodiphenyl-methane etc.
Surfactant in sizing agent of the present invention (as organic ammonium salt), in sizing agent, be as emulsifying agent, the organic emulsification combination of two-phase for epoxy resin and water, lipophilic group in surfactant molecule and epoxy resin molecule are combined closely, hydrophilic radical in surfactant molecule and water molecules, make epoxy resin molecule and hydrone form comparatively stable micro emulsion grain by the connection function of surfactant molecule, these micro emulsion grains are comparatively evenly distributed in water.When being subject to the active forces such as ambient temperature variation, mechanical force, it is agglomerating that micro emulsion grain is assembled, and finally can make that profit two phase stratification is separated out, breakdown of emulsion.
In sizing agent of the present invention, ammonium chloride is as stabilizing agent; chloride leach is in water; after dissolving, chlorion and ammonium ion are because intermolecular force and electric charge graviational interaction can closely be dispersed in the skin of epoxy resin and the micro emulsion grain of hydrone formation; form one deck protection dispersion layer; thereby avoided the micro emulsion grain in sizing agent because the variation of external condition is assembled agglomerating; therefore there will not be that layering is separated out, the phenomenon of breakdown of emulsion, storage stability and the stability in use of the sizing agent greatly strengthening.
The present invention has following advantage and effect with respect to prior art:
1, owing to containing plasticized modifier anacardol and formaldehyde, use the carbon fiber after emulsion type carbon fiber sizing agent starching of the present invention, when using polyamine to become composite as the epoxy resin-base of curing agent is compound, anacardol in sizing agent transition zone and formaldehyde can react with polyamine, the modified multicomponent amine hardener that reaction generates and the epoxy resin generation curing reaction in sizing agent transition zone, thereby make sizing agent transition zone there is great toughness after solidifying, thereby sizing agent transition zone strengthens greatly to the switching performance of carbon fiber and matrix resin, with respect to its interlaminar shear strength of existing carbon fibre composite, improve approximately more than 30%, guaranteed that carbon fibre composite has higher overall performance.
2, owing to containing stabilizing agent inorganic ammonium salt, the storage stability of sizing agent of the present invention improves greatly, stores 3 years above emulsions and still can keep stable performance under normal temperature, there will not be layering and CONCENTRATION DISTRIBUTION uneven phenomenon; In sizing agent use procedure of the present invention, rotating speed that can 200r/min stirs the conveying, dilution etc. of carrying out sizing agent, and sizing agent there will not be layering, demulsifying phenomenon; Use the carbon fiber after sizing agent starching of the present invention, under normal temperature, store 5 years after carbon fiber surface sizing agent quality percentage composition unchanged; The carbon fibre composite that uses carbon fiber after sizing agent starching of the present invention to manufacture, under its normal temperature, store 2 years after mechanical property without significant change.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
An emulsion type carbon fiber sizing agent, is prepared by following steps:
The surfactant of 0.5g (Japanese emulsifying agent company/Nikon that 707-SF) is joined in the deionized water of 97g, and agitation as appropriate mixes it; The bisphenol A type epoxy resin, 0.3g anacardol, the 0.1g formaldehyde that add again 2g, the rotating speed with 1000r/min at 40 ℃ stirs 100min; Then at 40 ℃ with the rotating speed high speed shear emulsification 35min of 10000r/min; The ammonium chloride that finally adds 0.1g, the rotating speed with 1000r/min at 40 ℃ stirs 25min, obtains emulsion type carbon fiber sizing agent.
The structure of surfactant is as follows:
Japan emulsifying agent company/Nikon that 707-SF
Embodiment 2
An emulsion type carbon fiber sizing agent, is prepared by following steps:
The surfactant of 1.5g (0.75g mitsubishi rayon/BPEO20SON, 0.75g mitsubishi rayon/SPEO120SON) is joined in the deionized water of 92.2g, and agitation as appropriate mixes it; The bisphenol f type epoxy resin, 0.9g anacardol, the 0.1g formaldehyde that add again 5g, the rotating speed with 750r/min at 60 ℃ stirs 80min; Then at 60 ℃ with the rotating speed high speed shear emulsification 25min of 7500r/min; The ammonium chloride that finally adds 0.3g, the rotating speed with 750r/min at 60 ℃ stirs 20min, obtains emulsion type carbon fiber sizing agent.
The structure of surfactant is as follows:
Mitsubishi rayon/BPEO20SON
Mitsubishi rayon/SPEO120SON
Embodiment 3
An emulsion type carbon fiber sizing agent, is prepared by following steps:
The surfactant of 4.0g (2.0g polyethylene oxide alkyl ethers, 2.0g polyethylene glycol oxide alkyl phenylate) is joined in the deionized water of 83.2g, and agitation as appropriate mixes it; The novolac epoxy resin, 2.0g anacardol, the 0.2g formaldehyde that add again 10g, the rotating speed with 500r/min at 60 ℃ stirs 60min; Then at 60 ℃ with the rotating speed high speed shear emulsification 15min of 5000r/min; The ammonium chloride that finally adds 0.6g, the rotating speed with 500r/min at 60 ℃ stirs 15min, obtains emulsion type carbon fiber sizing agent.
Embodiment 4
An emulsion type carbon fiber sizing agent, is prepared by following steps:
The surfactant of 8.0g (polyethylene glycol oxide aliphatic acid amino ethers) is joined in the deionized water of 66.3g, and agitation as appropriate mixes it; The bisphenol A type epoxy resin, 4g anacardol, the 0.5g formaldehyde that add again 20g, the rotating speed with 500r/min at 80 ℃ stirs 60min; Then at 80 ℃ with the rotating speed high speed shear emulsification 15min of 5000r/min; The ammonium chloride that finally adds 1.2g, the rotating speed with 500r/min at 80 ℃ stirs 15min, obtains emulsion type carbon fiber sizing agent.
Embodiment 5
An emulsion type carbon fiber sizing agent, is prepared by following steps:
The surfactant of 11g (4g Mitsui NPES3030P, 4g polyol fatty acid ester, 3g polyoxyethylene fatty acid esters) is joined in the deionized water of 49.6g, and agitation as appropriate mixes it; The bisphenol f type epoxy resin, 7g anacardol, the 0.8g formaldehyde that add again 30g, the rotating speed with 750r/min at 40 ℃ stirs 100min; Then at 40 ℃ with the rotating speed high speed shear emulsification 35min of 7500r/min; The ammonium chloride that finally adds 1.6g, the rotating speed with 750r/min at 40 ℃ stirs 25min, obtains emulsion type carbon fiber sizing agent.
The structure of surfactant is as follows:
Mitsui NPES3030P
Embodiment 6
An emulsion type carbon fiber sizing agent, is prepared by following steps:
The surfactant of 14g (5g Japan emulsifying agent company/Nikon you 723-SF, 5g produce chemical industrial company/FO180EO6SON, 4g polyethylene glycol oxide polyol fatty acid ester daily) is joined in the deionized water of 30g, and agitation as appropriate mixes it; The bisphenol A type epoxy resin, 12.5g anacardol, the 1.5g formaldehyde that add again 40g, the rotating speed with 1000r/min at 80 ℃ stirs 80min; Then at 80 ℃ with the rotating speed high speed shear emulsification 25min of 10000r/min; The ammonium chloride that finally adds 2g, the rotating speed with 1000r/min at 80 ℃ stirs 20min, obtains emulsion type carbon fiber sizing agent.
The structure of surfactant is as follows:
Japan emulsifying agent company/Nikon that 723-SF
Daily output chemical industrial company/FO180EO6SON
Comparative example 1
An emulsion type carbon fiber sizing agent, is prepared by following steps:
The surfactant of 0.5g (Japanese emulsifying agent company/Nikon that 707-SF) is joined in the deionized water of 97.5g, and agitation as appropriate mixes it; The bisphenol A type epoxy resin that adds again 2g, the rotating speed with 1000r/min at 40 ℃ stirs 100min; Then at 40 ℃ with the rotating speed high speed shear emulsification 35min of 10000r/min; Finally at 40 ℃, the rotating speed with 1000r/min stirs 25min, obtains emulsion type carbon fiber sizing agent.
Comparative example 2
An emulsion type carbon fiber sizing agent, is prepared by following steps:
The surfactant of 1.5g (0.75g mitsubishi rayon/BPEO20SON, 0.75g mitsubishi rayon/SPEO120SON) is joined in the deionized water of 93.5g, and agitation as appropriate mixes it; The bisphenol f type epoxy resin that adds again 5g, the rotating speed with 750r/min at 60 ℃ stirs 80min; Then at 60 ℃ with the rotating speed high speed shear emulsification 25min of 7500r/min; Finally at 60 ℃, the rotating speed with 750r/min stirs 20min, obtains emulsion type carbon fiber sizing agent.
Comparative example 3
An emulsion type carbon fiber sizing agent, is prepared by following steps:
The surfactant of 4.0g (2.0g polyethylene oxide alkyl ethers, 2.0g polyethylene glycol oxide alkyl phenylate) is joined in the deionized water of 86g, and agitation as appropriate mixes it; The novolac epoxy resin that adds again 10g, the rotating speed with 500r/min at 60 ℃ stirs 60min; Then at 60 ℃ with the rotating speed high speed shear emulsification 15min of 5000r/min; Finally at 60 ℃, the rotating speed with 500r/min stirs 15min, obtains emulsion type carbon fiber sizing agent.
Comparative example 4
An emulsion type carbon fiber sizing agent, is prepared by following steps:
The surfactant of 8.0g (polyethylene glycol oxide aliphatic acid amino ethers) is joined in the deionized water of 72g, and agitation as appropriate mixes it; The bisphenol A type epoxy resin that adds again 20g, the rotating speed with 500r/min at 80 ℃ stirs 60min; Then at 80 ℃ with the rotating speed high speed shear emulsification 15min of 5000r/min; Finally at 80 ℃, the rotating speed with 500r/min stirs 15min, obtains emulsion type carbon fiber sizing agent.
Comparative example 5
An emulsion type carbon fiber sizing agent, is prepared by following steps:
The surfactant of 11g (4g Mitsui NPES3030P, 4g polyol fatty acid ester, 3g polyoxyethylene fatty acid esters) is joined in the deionized water of 59g, and agitation as appropriate mixes it; The bisphenol f type epoxy resin that adds again 30g, the rotating speed with 750r/min at 40 ℃ stirs 100min; Then at 40 ℃ with the rotating speed high speed shear emulsification 35min of 7500r/min; Finally at 40 ℃, the rotating speed with 750r/min stirs 25min, obtains emulsion type carbon fiber sizing agent.
Comparative example 6
An emulsion type carbon fiber sizing agent, is prepared by following steps:
The surfactant of 14g (5g Japan emulsifying agent company/Nikon you 723-SF, 5g produce chemical industrial company/FO180EO6SON, 4g polyethylene glycol oxide polyol fatty acid ester daily) is joined in the deionized water of 46g, and agitation as appropriate mixes it; The bisphenol A type epoxy resin that adds again 40g, the rotating speed with 1000r/min at 80 ℃ stirs 80min; Then at 80 ℃ with the rotating speed high speed shear emulsification 25min of 10000r/min; Finally at 80 ℃, the rotating speed with 1000r/min stirs 20min, obtains emulsion type carbon fiber sizing agent.
By its stability of visual observations after storing 3 years under the sizing agent normal temperature of embodiment, the rotating speed with 200r/min in use stirs its stability of visual observations, and performance is listed in table 1.
Use the sizing agent of embodiment to impregnated carbon fiber starching, sizing agent quality is 0.1% of carbon fiber gross mass, surveys its sizing agent mass percent after storing 5 years under normal temperature, lists in table 2.The detection method of sizing agent content is GB/T26752-2011 polyacrylonitrile-based carbon fibre.
Use the carbon fiber after the starching of embodiment sizing agent to make epoxy resin base carbon fiber composite material, epoxy resin-base is used ethylenediamine as curing agent, measures the interlaminar shear strength (ILSS) of gained carbon fibre composite; After storing 2 years under normal temperature, survey its interlaminar shear strength, list in table 3.The detection method of composite interlayer shear strength is that JC/T773-2010 fibre reinforced plastics short beam method is measured interlaminar shear strength.
By its stability of visual observations after storing 15 months under the sizing agent normal temperature of comparative example, the rotating speed with 30r/min in use stirs its stability of visual observations, and performance is listed in table 1.
Use the sizing agent of comparative example to impregnated carbon fiber starching, sizing agent quality is 5% of carbon fiber gross mass, surveys its sizing agent mass percent after storing 5 years under normal temperature, lists in table 2.The detection method of sizing agent content is GB/T26752-2011 polyacrylonitrile-based carbon fibre.
Use the carbon fiber after the starching of comparative example sizing agent to make epoxy resin base carbon fiber composite material, epoxy resin-base is used ethylenediamine as curing agent, measures the interlaminar shear strength (ILSS) of gained carbon fibre composite; After storing 2 years under normal temperature, survey its interlaminar shear strength, list in table 3.The detection method of composite interlayer shear strength is that JC/T773-2010 fibre reinforced plastics short beam method is measured interlaminar shear strength.
The stability of table 1 sizing agent
Table 2 carbon fiber sizing agent changes of contents
Table 3 carbon fibre composite interlaminar shear strength
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 |
| Interlaminar shear strength/MPa | 110.41 | 109.88 | 110.56 | 109.32 | 110.68 | 110.14 |
| Store interlaminar shear strength/MPa after 2 years | 110.03 | 109.31 | 110.22 | 108.95 | 110.11 | 109.75 |
| Comparative example | 1 | 2 | 3 | 4 | 5 | 6 |
| Interlaminar shear strength/MPa | 82.55 | 82.88 | 81.71 | 82.68 | 81.85 | 81.49 |
| Store interlaminar shear strength/MPa after 2 years | 63.26 | 62.98 | 62.09 | 61.77 | 62.71 | 62.44 |
In all embodiment, all added plasticized modifier anacardol and formaldehyde and stabilizing agent ammonium chloride, and all do not added in comparative example, all the other component ratios are identical.
By table 1, can find out: added the storage stability of sizing agent after stabilizing agent ammonium chloride and greatly strengthened, and in use procedure, stability during agitation and dilution is also strengthened greatly, can stir and dilute with rotating speed more than 200r/min.
By table 2, can find out: added the sizing agent of stabilizing agent ammonium chloride, after using it to carbon fiber starching, the sizing agent storage stability of carbon fiber surface strengthens greatly.
By table 3, can find out: the sizing agent that has added plasticized modifier anacardol and formaldehyde and stabilizing agent ammonium chloride, the carbon fibre composite that uses the carbon fiber after its starching to make, the mechanical properties such as its interlaminar shear strength have great increase, and after carbon fibre composite stores 2 years, shear strength is substantially unchanged, and its storage stability strengthens greatly.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. an emulsion type carbon fiber sizing agent, is characterized in that the composition that contains following mass percent:
Epoxy resin: 2-40%
Water: 0-97%
Surfactant: 0.5-14%
Anacardol: 0.3-12.5%
Formaldehyde: 0.1-1.5%
Inorganic ammonium salt: 0.1-2.0%;
Wherein, the mass percent of water is not 0.
2. emulsion type carbon fiber sizing agent according to claim 1, is characterized in that: described epoxy resin is a kind of in bisphenol A type epoxy resin, bisphenol f type epoxy resin or novolac epoxy resin.
3. emulsion type carbon fiber sizing agent according to claim 1, is characterized in that: described surfactant is anion surfactant and/or non-ionic surface active agent.
4. emulsion type carbon fiber sizing agent according to claim 1, is characterized in that: described inorganic ammonium salt is a kind of in ammonium chloride, ammonium sulfate or ammonium nitrate.
5. emulsion type carbon fiber sizing agent according to claim 1, is characterized in that: described inorganic ammonium salt is ammonium chloride.
6. the preparation method of sizing agent for the emulsion type carbon fiber described in claim 1-5 any one, it is characterized in that comprising the following steps: surfactant is soluble in water, add again epoxy resin, anacardol, formaldehyde, under 500-1000r/min, stir 60-100min; Then at 5000-10000r/min down cut emulsification 15-35min; Finally add inorganic ammonium salt, under 500-1000r/min, stir 15-25 min, obtain emulsion type carbon fiber sizing agent.
7. the application in making epoxy resin base carbon fiber composite material with sizing agent of the emulsion type carbon fiber described in claim 1-5 any one.
8. a carbon fiber, is characterized in that: contain the emulsion type carbon fiber sizing agent described in claim 1-5 any one, emulsion type carbon fiber is the 0.1-5% of carbon fiber quality by the quality of sizing agent.
9. an epoxy resin base carbon fiber composite material, is characterized in that: contain carbon fiber claimed in claim 8, epoxy resin-base is used polyamine as curing agent.
10. epoxy resin base carbon fiber composite material according to claim 9, is characterized in that: described polyamine is ethylenediamine, hexamethylene diamine, diethylenetriamine, m-phenylene diamine (MPD), triethylene tetramine or diaminodiphenyl-methane.
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| CN101091010A (en) * | 2004-12-27 | 2007-12-19 | 东丽株式会社 | Oil agent for carbon fiber precursor fiber, carbon fiber and method for producing carbon fiber |
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