WO2015046030A1 - 繊維強化複合材料用2液型エポキシ樹脂組成物および繊維強化複合材料 - Google Patents
繊維強化複合材料用2液型エポキシ樹脂組成物および繊維強化複合材料 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—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
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—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 catalysts used
- C08G59/686—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 catalysts used containing nitrogen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—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 catalysts used
- C08G59/688—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 catalysts used containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2463/02—Polyglycidyl ethers of bis-phenols
Definitions
- the present invention relates to a two-pack type epoxy resin composition used for a fiber-reinforced composite material, and a fiber-reinforced composite material using the same.
- Fiber reinforced composite materials composed of reinforced fibers and matrix resins can be designed using the advantages of reinforced fibers and matrix resins, so the applications are expanding to aerospace, sports and general industrial fields. .
- the reinforcing fiber glass fiber, aramid fiber, carbon fiber, boron fiber, etc. are used.
- the matrix resin either a thermosetting resin or a thermoplastic resin is used, but a thermosetting resin that can be easily impregnated into the reinforcing fiber is often used.
- the thermosetting resin epoxy resin, unsaturated polyester resin, vinyl ester resin, phenol resin, bismaleimide resin, cyanate resin and the like are used.
- the RTM method is to close the mold after placing the reinforcing fiber base in the mold, inject the resin from the resin injection port, impregnate the reinforcing fiber, harden the resin, open the mold and take out the molded product.
- productivity is a major issue in disseminating carbon fiber composite materials to automobiles, which becomes a barrier, and carbon fiber composite materials are only slightly used in some high-end vehicles.
- the two-pack type epoxy resin composition is composed of a main agent liquid containing an epoxy resin as a main component and a hardener liquid containing a curing agent as a main component, and two liquids of the main agent liquid and the hardener liquid are mixed immediately before use. It is the epoxy resin composition obtained by this.
- an epoxy resin composition in which all components including a main agent and a curing agent are mixed together in advance is referred to as a one-pack type epoxy resin composition.
- a solid material having low reactivity is often selected as the curing agent component, and a press roll or the like is used to impregnate the reinforcing fiber with the one-pack type epoxy resin composition.
- a press roll or the like is used to impregnate the reinforcing fiber with the one-pack type epoxy resin composition.
- the mixture of the main agent liquid and the curing agent liquid can be made into a low-viscosity liquid by making both the main agent liquid and the curing agent liquid liquid, and impregnating the reinforcing fibers. It becomes easy to make. Further, since the main agent liquid and the curing agent liquid are stored separately, long-term storage is possible without any particular limitation on the storage conditions.
- the resin curing time is short, but also the following five requirements are satisfied at once. Is specifically required.
- the first requirement is that, during the mixing and preparing operation of the resin raw material, both of the two liquids are low in viscosity and close in viscosity level, thereby being excellent in mixing workability.
- the second requirement is that the resin composition after mixing and preparation is stable with an increase in viscosity for a long time while being kept at a low temperature, that is, excellent in viscosity stability.
- the third requirement is that the resin composition has a low viscosity during the resin injecting step to the reinforcing fiber base, and the increase in viscosity is suppressed during the injecting step, whereby the reinforcing fiber base It has excellent impregnation properties.
- the fourth requirement is that sufficient high-speed curing can be achieved in the low temperature region around 100 ° C, thereby simplifying the molding equipment and eliminating the need to use auxiliary materials with high heat resistance, thereby reducing costs. As well as being able to reduce thermal shrinkage derived from the temperature difference between the curing temperature and normal temperature, the surface smoothness of the molded product is excellent.
- the fifth requirement is that during the demolding process after molding, the resin has reached sufficient rigidity due to curing, and is less likely to be distorted, thereby enabling smooth demolding and further the painting process. High dimensional accuracy can be obtained in the molded product without causing distortion or deformation even after passing.
- Patent Document 1 discloses a fiber-reinforced composite that can be cured in a short time at a low temperature and has a molded product having excellent rigidity by containing a polyol having an aromatic ring in the epoxy resin composition.
- An epoxy resin composition suitable for molding a material is disclosed. However, this epoxy resin composition did not have sufficient viscosity stability in the low temperature region.
- Patent Document 2 discloses that an epoxy resin composition using an acid anhydride as a curing agent and an organic phosphorus compound as a catalyst in combination with a low viscosity retention time and curing under a constant temperature condition near 100 ° C.
- a technique for achieving an excellent time balance is disclosed.
- this technique has a problem that the high-speed curability is not sufficient, and the rigidity of the resin at the time of demolding is not sufficient, and the dimensional accuracy may be lowered.
- Patent Document 3 discloses that the toughness of a cured resin is obtained by combining an epoxy resin obtained by hydrogenating an aromatic epoxy resin as a main agent, an acid anhydride as a curing agent, and an aliphatic polyol having 16 to 60 carbon atoms. , The generation of cracks due to the thermal cycle has been improved, and a technique for making an epoxy resin composition for a semiconductor sealing material excellent in weather resistance has been disclosed, but this technique also does not have sufficient high-speed curability, It was not suitable for fiber reinforced composite applications.
- the RTM method can be executed in a high cycle (shortening the time required for one molding cycle and increasing the molding cycle to be executed within a certain period of time), and it is necessary to realize a high level of productivity.
- JP 2010-163573 A International Publication No. 2007/125759 JP 2002-69155 A
- the purpose of the present invention is to improve the disadvantages of the prior art, to improve the workability during resin preparation, to provide excellent viscosity stability at low temperatures after resin preparation, and to maintain a low viscosity when injected into reinforcing fibers.
- the two-pack type epoxy resin composition for fiber-reinforced composite material of the present invention has the following configuration. That is, a two-component epoxy for fiber-reinforced composite material containing the following components [A] to [D] and having a mass blending ratio of component [A] and component [B] of 5:95 to 50:50 It is a resin composition.
- Organophosphorus compound or imidazole derivative Organophosphorus compound or imidazole derivative
- the fiber-reinforced composite material of the present invention has the following configuration. That is, it is a fiber-reinforced composite material obtained by combining and curing the above-described two-component epoxy resin composition for fiber-reinforced composite material and reinforcing fibers.
- the two-pack type epoxy resin composition of the present invention is not only excellent in workability at the time of resin preparation, but also has excellent viscosity stability at low temperatures of the resin composition. It has excellent impregnation properties and can be cured in a short time during molding.
- the two-pack type epoxy resin composition of the present invention it becomes possible to provide a fiber-reinforced composite material having high dimensional accuracy and excellent heat resistance with high productivity.
- the two-component epoxy resin composition according to the present invention includes the following components [A] to [D].
- Component [A] and Component [B] are both epoxy resins.
- An epoxy resin is a compound having one or more epoxy groups in one molecule.
- the epoxy resin of component [A] needs to have an epoxy equivalent of 250 or less and a hydroxyl group equivalent of 500 or less. Since the epoxy resin of component [A] has an epoxy equivalent of 250 or less, the epoxy resin composition using the epoxy resin has a reduced viscosity and good impregnation into reinforcing fibers, and the resulting fiber reinforced The composite material has excellent heat resistance. In addition, when an epoxy resin having an epoxy equivalent that is too small is used as the component [A], it may contain low molecular weight impurities, and in the resulting fiber-reinforced composite material, surface quality due to volatilization of impurities during molding. May lead to deterioration. Therefore, the epoxy resin of component [A] preferably has an epoxy equivalent of 110 or more.
- the hydroxyl group equivalent indicates the molecular weight of the epoxy resin per hydroxyl group in the epoxy resin, that is, the smaller the value, the larger the hydroxyl amount per molecule. Since the epoxy resin of component [A] has a hydroxyl group equivalent of 500 or less, as will be described later, the amount of hydroxyl groups in the molecular structure of the epoxy resin increases, and the effect of improving the curing rate is exhibited. In addition, when an epoxy resin having a hydroxyl group equivalent too small is used as component [A], the amount of hydroxyl groups in the molecular structure of the epoxy resin is excessively increased as described later, and viscosity stability described later may be lowered. is there.
- the epoxy resin of component [A] preferably has a hydroxyl group equivalent of 150 or more.
- the hydroxyl group contained in component [A] is preferably an alcoholic hydroxyl group, and the epoxy resin of component [A] preferably has two or more epoxy groups from the viewpoint of improving the heat resistance of the cured product. More preferably, it is 2 or more and 5 or less.
- component [A] include aromatic glycidyl ethers obtained by reacting phenols having a plurality of hydroxyl groups with alkyl halides having an epoxy group such as epichlorohydrin, and epichlorohydrides to polyols having a plurality of hydroxyl groups.
- alkyl halides having an epoxy group such as epichlorohydrin
- epichlorohydrides to polyols having a plurality of hydroxyl groups.
- aliphatic glycidyl ethers obtained by reacting an alkyl halide having an epoxy group such as phosphorus and having an epoxy equivalent and a hydroxyl equivalent within the above range.
- Component [A] is an aliphatic glycidyl ether derived from a polyol, ie, a polyol having a plurality of hydroxyl groups, from the viewpoint of improving the impregnation property to the reinforcing fiber base by suppressing the composition viscosity to a low viscosity.
- An aliphatic glycidyl ether obtained by reacting an alkyl halide having an epoxy group such as phosphorus is preferable.
- aliphatic glycidyl ethers examples include glycidyl ether of glycerin, glycidyl ether of trimethylolethane, glycidyl ether of trimethylolpropane, glycidyl ether of sorbitol, glycidyl ether of diglycerol, and the like.
- diglycidyl ether of glycerin that is, glycerin type epoxy resin, glycidyl ether of trimethylolpropane, that is, trimethylolpropane type epoxy resin, glycidyl ether of sorbitol, that is, sorbitol type epoxy resin, glycidyl ether of diglycerol, that is, diglycerol type
- the epoxy resin is particularly preferably used as the component [A] because it is excellent in the balance between the viscosity of the resin composition and the heat resistance of the resulting cured resin and the mechanical properties such as the elastic modulus.
- Component [A] contributes to the improvement of the curing rate by the progress of the ring-opening reaction when the hydroxyl group in its molecular structure reacts with the epoxy group and the acid anhydride group.
- an alcohol having no epoxy group is added instead of the component [A]
- the curing rate accompanying the ring opening of the epoxy group and the acid anhydride group is improved by the hydroxyl group, but the viscosity stability described later is remarkably high.
- the workability during molding is reduced.
- the presence of hydroxyl groups in the molecular structure of the epoxy resin as in component [A] limits the movement of hydroxyl groups compared to the addition of alcohols without epoxy groups, thus increasing viscosity stability It is thought that it can be done.
- glycerin type epoxy resins include “Denacol” (registered trademark) EX-313, EX-314 (both manufactured by Nagase ChemteX Corp.), “Araldite” (registered trademark) DY-S (manufactured by Huntsman), etc. Is mentioned.
- trimethylolpropane type epoxy resins examples include “Denacol” (registered trademark) EX-321 (manufactured by Nagase ChemteX Corporation).
- sorbitol-type epoxy resins examples include “Denacol” (registered trademark) EX-611 and EX-614B (both manufactured by Nagase ChemteX Corporation).
- diglycerol type epoxy resins examples include “Denacol” (registered trademark) EX-421 (manufactured by Nagase ChemteX Corporation).
- aromatic glycidyl ether corresponding to component [A] include an alkyldiphenol type epoxy resin having a hydroxyl group, and a commercially available product thereof is “EPICLON” (registered trademark) HP-820 (DIC Corporation). ))).
- the hydroxyl group equivalent of the epoxy resin is a hydroxyl value measured by a pyridine-acetyl chloride method in accordance with JIS K 0070 (1992) (necessary for neutralizing acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated). Is the reciprocal of the value obtained by dividing the number of mg of potassium hydroxide in mgKOH / g) by the formula weight of potassium hydroxide (56.11), which corresponds to the molecular weight per hydroxyl group (units). : G / eq).
- the “pyridine-acetyl chloride method” for measuring the hydroxyl equivalent of an epoxy resin involves dissolving the measurement resin in pyridine, adding an acetyl chloride-toluene solution, heating, cooling, and further boiling to obtain excess acetyl chloride. Then, the acetic acid produced was titrated with a potassium hydroxide ethanol solution and measured.
- Component [B] is an epoxy resin other than component [A], that is, at least an epoxy resin having an epoxy equivalent of more than 250 or an epoxy resin having a hydroxyl equivalent of more than 500. In addition, it is preferable that the epoxy equivalent of the epoxy resin of component [B] is 1000 or less.
- component [B] examples include an aromatic glycidyl ether obtained from a phenol having a plurality of hydroxyl groups, an aliphatic glycidyl ether obtained from an alcohol having a plurality of hydroxyl groups, a glycidyl amine obtained from an amine, an epoxy resin having an oxirane ring, Examples thereof include glycidyl esters obtained from carboxylic acids having a plurality of carboxyl groups and having epoxy equivalents and hydroxyl equivalents in the above-described ranges.
- aromatic glycidyl ethers that can be used as component [B] are obtained from bisphenols such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol AD, and diglycidyl ether of bisphenol S.
- Diglycidyl ether novolak polyglycidyl ether obtained from phenol, alkylphenol, etc., resorcinol diglycidyl ether, hydroquinone diglycidyl ether, 4,4′-dihydroxybiphenyl diglycidyl ether, 4,4′-dihydroxy-3 , 3 ′, 5,5′-tetramethylbiphenyl diglycidyl ether, 1,6-dihydroxynaphthalene diglycidyl ether, 9,9′-bis (4- Roxyphenyl) fluorene diglycidyl ether, tris (p-hydroxyphenyl) methane triglycidyl ether, tetrakis (p-hydroxyphenyl) ethane tetraglycidyl ether, bisphenol A diglycidyl ether and bifunctional isocyanate And diglycidyl ether having an oxazolidone skeleton.
- aliphatic glycidyl ethers that can be used as component [B] include diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol, diglycidyl ether of 1,4-butanediol, and 1,6-hexanediol.
- Diglycidyl ether diglycidyl ether of neopentyl glycol, diglycidyl ether of cyclohexanedimethanol, triglycidyl ether of glycerin, triglycidyl ether of trimethylolethane, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of pentaerythritol, dodeca Examples thereof include diglycidyl ether of hydrobisphenol A and diglycidyl ether of dodecahydrobisphenol F.
- glycidylamine examples include diglycidylaniline, diglycidyltoluidine, triglycidylaminophenol, tetraglycidyldiaminodiphenylmethane, tetraglycidylxylylenediamine, halogens thereof, alkyl-substituted products, water Examples include accessories.
- Examples of the epoxy resin having an oxirane ring that can be used as the component [B] include vinylcyclohexene dioxide, dipentene dioxide, 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexylmethyl, and adipate bis ( 3,4-epoxycyclohexylmethyl), dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, oligomers of 4-vinylcyclohexene dioxide, and the like.
- glycidyl esters that can be used as component [B] include phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, and dimer acid diglycidyl ester.
- diglycidyl ethers of bisphenol compounds that is, bisphenol type epoxy resins, particularly bisphenol A type epoxy resins, have a balance between the viscosity of the resin composition and the heat resistance of the resulting cured resin and mechanical properties such as elastic modulus. Since it is excellent, it is preferably used as component [B].
- the bisphenol A type epoxy resin suitably used as component [B] preferably has a repeating unit number in the range of 0 to 0.2, more preferably in the range of 0 to 0.1.
- the number of such repeating units corresponds to n in the chemical structural formula of the bisphenol A type epoxy resin usually represented by the following formula.
- the number of such repeating units exceeds 0.2, the viscosity of the epoxy resin composition increases and the impregnation property to the reinforcing fibers is deteriorated, and the heat resistance of the obtained fiber-reinforced composite material may be insufficient. .
- the bisphenol A type epoxy resin suitably used as the component [B] preferably has an epoxy equivalent in the range of 170 to 220, and more preferably in the range of 170 to 195.
- an epoxy equivalent usually has a relationship such that it increases as the number of repeating units increases and decreases as it decreases. If the epoxy equivalent is too small, low molecular weight impurities may be contained, which may lead to deterioration of the surface quality due to volatilization during molding. On the other hand, if the epoxy equivalent is too large, the viscosity of the epoxy resin composition is increased, the impregnation property of the reinforcing fibers is deteriorated, and the resulting fiber-reinforced composite material may have insufficient rigidity.
- the mass blending ratio of the component [A] and the component [B] needs to be 5:95 to 50:50, and is preferably 10:90 to 35:65.
- the amount of the component [A] is too small, the time required for curing becomes long and the productivity is lowered.
- the amount of [B] is too small, the heat resistance of the cured product is lowered or the viscosity stability of the resin composition is lowered. To do.
- the amount of hydroxyl groups in the resin composition is preferably 0.1 mol / kg to 1.0 mol / kg, More preferably, it is not less than kg and not more than 0.6 mol / kg. If the amount of the hydroxyl group in 1 kg of the epoxy resin composition is too small, the effect of the hydroxyl group is not manifested and the time required for curing may become long and the productivity may be lowered. If too much, the viscosity stability of the resin composition may be reduced. May decrease.
- the amount of hydroxyl groups in the resin composition can be calculated using the following formula.
- COH ( ⁇ (wn / wnOH)) / W ⁇ 1000 (Expression 1)
- COH Amount of hydroxyl groups in the epoxy resin composition (mol / kg)
- wn part by mass of each component
- wnOH hydroxyl equivalent (g / eq) of each component
- W Sum of mass parts of all components
- the amount of hydroxyl groups in the resin composition may be calculated by Formula 1 using a hydroxyl group equivalent for each component constituting the main agent liquid and the curing agent liquid, and the hydroxyl groups of the entire main agent liquid and the entire curing agent liquid. Equivalents were respectively measured by the above-mentioned “pyridine-acetyl chloride method” to obtain “hydroxyl equivalents of the main agent liquid” and “hydroxyl equivalents of the curing agent liquid”, and calculated by the formula (1) using them as components. May be.
- Component [C] is an acid anhydride, specifically a carboxylic acid anhydride, and more specifically a compound having at least one carboxylic acid anhydride group capable of reacting with an epoxy group of an epoxy resin in one molecule. It acts as a curing agent for epoxy resin.
- the number of carboxylic anhydride groups is desirably 4 or less per molecule.
- Component [C] may be an acid anhydride having an aromatic ring but no alicyclic structure such as phthalic anhydride, or an aromatic ring or alicyclic structure such as succinic anhydride. Although it may be an acid anhydride that does not have any of the above, it should be an acid anhydride having a cycloaliphatic structure from the viewpoint of heat resistance and mechanical properties of the cured product. Among them, an acid anhydride having a cycloalkane ring or a cycloalkene ring is more preferable.
- acid anhydrides having an alicyclic structure include hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyldihydronadic acid anhydride, 1,2,4,5-cyclopentanetetracarboxylic acid Dianhydride, 1,2,3,6-tetrahydrophthalic anhydride, methyl-1,2,3,6-tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, bicyclo [2,2 , 2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -3-methyl-1,2,5, Examples include 6-tetrahydrophthalic anhydride.
- those selected from hexahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride and their alkyl-substituted types are the viscosity of the resin composition, the heat resistance of the resulting cured resin, and the elastic modulus. Therefore, it is preferably used as the component [C]. Even when an acid anhydride having an alicyclic structure is used as the component [C], the epoxy resin composition according to the present invention contains an acid anhydride having no alicyclic structure. Also good.
- the compounding amount of all epoxy resins (component [A] and component [B]) and component [C] is the number of acid anhydride groups (H) in component [C] and the total number of epoxy groups (E) in all epoxy resins.
- the H / E ratio is preferably in the range of 0.8 to 1.1, more preferably in the range of 0.85 to 1.05, and still more preferably in the range of 0.9 to 1.0. Try to meet.
- the H / E ratio is too small, the polymerization between the excessively existing epoxy resins proceeds, leading to a decrease in physical properties of the cured product. If the H / E ratio is too large, the concentration of the reaction point of the system decreases due to the excessive curing agent component, the reaction rate decreases, and sufficient high-speed curability may not be exhibited.
- the epoxy resin composition according to the present invention needs to contain an organophosphorus compound or an imidazole derivative as component [D], which acts as a curing accelerator for rapid curing.
- component [D] acts as a curing accelerator for rapid curing.
- the detailed mechanism of the organophosphorus compound and the imidazole derivative is not clear, it has an action of suppressing the progress of the reaction at the initial stage of the curing reaction of the epoxy resin composition, while the time for the epoxy resin composition to maintain a low viscosity is prolonged. In the middle and late stages of the curing reaction, the reaction rate is considered to be sufficiently high so that the curing time can be shortened.
- Component [D] is preferably blended in an amount of 5 to 25 parts by weight, more preferably 10 to 22 parts by weight, based on 100 parts by weight of the total epoxy resin including component [A] and component [B]. . If the amount of component [D] is too small, the time required for curing becomes long and sufficient high-speed curability cannot often be exhibited. On the other hand, when there are too many compounding quantities of component [D], the time which maintains a low viscosity will become short and the impregnation to a reinforced fiber will become difficult in many cases. By using the component [C] and the component [D] for the curing agent and the curing accelerator, it is possible to achieve both speed improvement and viscosity stability for the first time by the component [A].
- organic phosphorus compounds include tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris (4-methoxyphenyl) phosphine, tris (2,6-dimethoxyphenyl) phosphine, diphenylcyclohexylphosphine, p-styryldiphenylphosphine, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) ) Propane, 1,4-bis (diphenylphosphino) butane, tetraphenylphosphonium / tetraphenylborate, triphenylphosphine / triphenyl
- imidazole derivatives include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2- Phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1 -Cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole and the like.
- the above-described components are properly blended so that the viscosity at 25 ° C. is 0.1 to 2.5 Pa ⁇ s, preferably 0.1 to 2.0 Pa. -It is more preferable to set it as s.
- the viscosity at 25 ° C. is 0.1 to 2.5 Pa ⁇ s, preferably 0.1 to 2.0 Pa.
- -It is more preferable to set it as s.
- the viscosity at the molding temperature does not become too low, and it is possible to prevent pits generated by entraining air when injected into the reinforcing fiber base material. It is possible to prevent the occurrence of an unimpregnated region caused by non-uniformity.
- the viscosity at 25 ° C. is measured immediately after the adjustment of the epoxy resin composition.
- the pot life after mixing all the components is important, and viscosity stability is required.
- the value of the ratio of the viscosity at 40 ° C. immediately after mixing all components to 40 ° C. for 20 minutes and the viscosity at 40 ° C. immediately after mixing all components is N
- the resin composition It is preferable to have a specific temperature T that satisfies N ⁇ t90 ⁇ 12, where t90 (unit: minute) is the time at which the cure index obtained by dielectric measurement when holding an object at a constant temperature T is 90%. .
- the viscosity is obtained by measuring, for example, based on a measuring method using a cone-plate type rotational viscometer in ISO 2884-1 (1999).
- the measuring apparatus include TVE-33H type manufactured by Toki Sangyo Co., Ltd.
- t10 and t90 are the following three. It is preferable to have a specific temperature T ′ that satisfies all of the relational expressions (Expression 2) to (Expression 4).
- t10 represents the time (minutes) from the start of measurement at the temperature T ′ until the cure index reaches 10%
- t90 represents the time (minutes) from the start of measurement to the cure index reaching 90%. To express.).
- Dielectric measurement cannot be uniquely associated with viscosity and elastic modulus, but is useful for obtaining a curing profile of a thermosetting resin that changes from a low-viscosity liquid to a high-elasticity amorphous solid.
- a curing profile is obtained as a time change of ion viscosity (equivalent resistivity) calculated from a complex dielectric constant measured by applying a high-frequency electric field to a thermosetting resin.
- an MDE-10 cure monitor manufactured by Holometrix-Micromet can be used as the dielectric measurement device.
- a Viton O-ring having an inner diameter of 32 mm and a thickness of 3 mm is installed on the lower surface of the programmable mini press MP2000 with a TMS-1 inch type sensor embedded in the lower surface, and the press temperature is set to a predetermined temperature T ′. Set to.
- the epoxy resin composition is poured inside the O-ring, the press is closed, and the time change of the ionic viscosity of the resin composition is followed. Dielectric measurement is performed at frequencies of 1, 10, 100, 1000, and 10000 Hz, and the logarithm Log ( ⁇ ) of ion viscosity independent of frequency is obtained by using software (Umetric) attached to the apparatus.
- the cure index at the curing time t is obtained by (Equation 5).
- the time for the cure index to reach 10% is t10, and the time for the cure index to reach 90% is t90.
- Cure index ⁇ log ( ⁇ t) ⁇ log ( ⁇ min) ⁇ / ⁇ log ( ⁇ max) ⁇ log ( ⁇ min) ⁇ ⁇ 100 (Expression 5)
- ion viscosity by dielectric measurement is relatively easy even if the curing reaction is fast.
- the ionic viscosity can be measured after gelation, and increases with the progress of curing, and saturates with the completion of curing. Therefore, not only the initial viscosity change but also the progress of the curing reaction is tracked. Can also be used.
- the value obtained by standardizing the logarithm of the ionic viscosity so that the minimum value is 0% and the saturation value (maximum value) is 100% is called the cure index, and describes the curing profile of the thermosetting resin. Used to do.
- the initial viscosity increase is small and short. Preferred conditions can be described for curing in time.
- t10 proportional to the time (flowable time) at which the epoxy resin composition can flow at the specific temperature T ′ is 0.5 minutes to 4 minutes (Formula 2)
- Curing of the epoxy resin composition is almost completed
- t90, which is proportional to the time when demolding is possible is 0.5 minutes to 9 minutes (Formula 3)
- the ratio of time to flowable time is greater than 1 and not more than 2.5 (Equation 4). That is, in the above range, when t10 is large, the epoxy resin composition is easily impregnated into the reinforcing fiber base, and when t90 is small, it means that the epoxy resin composition is cured quickly. Therefore, t90 / t10 is 1 The smaller one is more preferable in the range of 2.5 or less.
- the molding temperature (heat curing temperature) of the epoxy resin composition that is, the specific temperature T or T ′ is preferably in the range of 90 to 130 ° C.
- the specific temperature T or T ' is in the range of 90 to 130 ° C, so that the time required for curing is shortened, and at the same time, the thermal shrinkage after demolding is alleviated, so that the fiber reinforced composite has good surface quality. Material can be obtained.
- the two-pack type epoxy resin composition of the present invention first comprises the above-mentioned blending amounts of a main agent liquid containing component [A] and component [B] as main components and a curing agent solution containing component [C] as main components. Each of them is prepared by mixing them together, and the main agent solution and the curing agent solution are mixed so as to obtain the above-described amounts just before use.
- the above-mentioned component [D] may be blended in either the main agent liquid or the hardener liquid, but is usually included in the hardener liquid.
- Other ingredients may be formulated into either base material liquid, the sclerosant liquid may be used in admixture with either or both advance.
- the main component usually means 50% by mass, preferably 70% by mass, more preferably more than 90% by mass with respect to the whole, even if it is 100% by mass. good.
- the main agent liquid and the curing agent liquid should be heated separately before mixing, and mixing with a mixer immediately before use, such as pouring into a mold, to obtain an epoxy resin composition, It is preferable from the viewpoint of the pot life of the resin.
- the above-described two-component epoxy resin composition and reinforcing fibers are combined, and the epoxy resin composition is cured to obtain the fiber-reinforced composite material of the present invention.
- the molding method for obtaining the fiber-reinforced composite material of the present invention is not particularly limited, but there are molding methods using a two-component resin such as a hand layup method, a filament winding method, a pultrusion method, and an RTM method. Preferably used. Of these, the RTM method is particularly preferably used from the viewpoint of productivity and the degree of freedom of shape of a molded product. In the RTM method, a resin is injected into a reinforcing fiber base disposed in a mold and cured to obtain a reinforcing fiber composite material.
- the epoxy resin composition according to the present invention is obtained.
- the heated epoxy resin composition is injected and impregnated into a reinforcing fiber base disposed in a mold heated to a specific temperature T or T ′, It can be manufactured by curing.
- the temperature at which the epoxy resin composition is heated is determined from the relationship between the initial viscosity and the viscosity increase of the epoxy resin composition from the viewpoint of impregnation into the reinforcing fiber substrate, and is preferably 30 to 70 ° C., more preferably 50 ⁇ 60 ° C.
- a mold having a plurality of injection ports is used, and an epoxy resin composition is injected from a plurality of injection ports simultaneously or sequentially with a time difference. It is preferable to select an appropriate condition according to the fiber-reinforced composite material to be used, because it has a degree of freedom to cope with molded products having various shapes and sizes. There are no restrictions on the number or shape of such injection ports, but in order to enable injection in a short time, it is better that there are more injection ports, and the arrangement can shorten the flow length of the resin according to the shape of the molded product. Position is preferred.
- the injection pressure when injecting the epoxy resin composition is usually 0.1 to 1.0 MPa, and preferably 0.1 to 0.6 MPa in view of the injection time and the economical efficiency of the equipment.
- VaRTM Varum-Assisted Resin Transfer Molding
- glass fiber, aramid fiber, carbon fiber, boron fiber, or the like is preferably used as the reinforcing fiber.
- carbon fiber is preferably used because it is lightweight and a fiber-reinforced composite material having excellent mechanical properties such as strength and elastic modulus can be obtained.
- the reinforcing fiber may be either a short fiber or a continuous fiber, or both may be used in combination. In order to obtain a high Vf fiber-reinforced composite material, continuous fibers are preferred.
- the reinforcing fiber may be used in the form of a strand.
- a reinforcing fiber base material obtained by processing the reinforcing fiber into a form such as a mat, a woven fabric, a knit, a blade, or a unidirectional sheet is preferable. Used. Among them, a woven fabric which is easy to obtain a high Vf fiber-reinforced composite material and excellent in handleability is preferably used.
- the ratio of the net volume of the reinforcing fibers to the apparent volume of the fabric is defined as the fabric filling rate.
- the filling rate of the woven fabric is obtained from the weight per unit area W (unit: g / m 2 ), the thickness t (unit: mm), and the density ⁇ f (unit: g / cm 3 ) of the reinforcing fiber by the formula of W / (1000 t ⁇ ⁇ f). It is done.
- the fabric weight and thickness are determined in accordance with JIS R 7602 (1995). The higher the woven fabric filling rate, the easier it is to obtain a fiber reinforced composite material having a high Vf. Therefore, the woven fabric filling rate is 0.10 to 0.85, preferably 0.40 to 0.85, more preferably 0.50. It is preferably in the range of ⁇ 0.85.
- the fiber volume content Vf is preferably in the range of 40 to 85%, preferably 45 to 85%.
- the fiber volume content Vf of a fiber reinforced composite material said here is a value defined and measured by the following based on ASTM D3171 (1999), and is an epoxy resin with respect to a reinforced fiber base material. It refers to the state after the composition is injected and cured. That is, the fiber volume content Vf of the fiber reinforced composite material can be calculated from the thickness h of the fiber reinforced composite material using the following formula.
- Vf (%) (Af ⁇ N) / ( ⁇ f ⁇ h) / 10 (Expression 6)
- Af fiber base material one ⁇ 1 m 2 per mass (g / m 2)
- N Number of laminated fiber substrates (sheets)
- ⁇ f density of reinforcing fiber (g / cm 3 )
- h Thickness (mm) of the fiber reinforced composite material (test piece).
- the mass Af per fiber substrate / m 2 , the number N of laminated fiber substrates, and the density ⁇ f of reinforcing fibers can be specified from the fiber reinforced composite material. What is necessary is just to isolate
- the density of the reinforcing fiber used in this case a value measured based on JIS R 7603 (1999) is used.
- the thickness h of the fiber reinforced composite material is preferably measured with a micrometer specified in JIS B-7502 (1994) or having a precision equivalent to or higher than that described in JIS K-7707 (1991). . If the fiber reinforced composite material has a complicated shape and it is difficult to measure, cut out a sample (a sample with a certain shape and size for measurement) from the fiber reinforced composite material. You may measure.
- a veneer can be mentioned.
- a sandwich structure in which a single plate-like fiber reinforced composite material is disposed on both surfaces of the core material, a hollow structure in which the periphery is covered with a single plate-like structure, or a single plate-like fiber Examples include so-called canalling structures in which a reinforced composite material is disposed on one side of a core material.
- honeycomb cores made of aluminum or aramid foam cores made of polyurethane, polystyrene, polyamide, polyimide, polyvinyl chloride, phenol resin, acrylic resin, epoxy resin, etc.
- Examples include timber such as balsa.
- a foam core is preferably used as the core material because a lightweight fiber-reinforced composite material can be obtained.
- the fiber-reinforced composite material of the present invention is lightweight and excellent in mechanical properties such as strength and elastic modulus. Therefore, it is preferably used for structural members and outer plates of aircraft, space satellites, industrial machines, railway vehicles, ships, automobiles, etc. It is done. Moreover, since it is excellent also in a color tone, surface quality, and dimensional accuracy, it is preferably used especially for an automobile outer plate.
- Epoxy Resin “Denacol” (registered trademark) EX-313 manufactured by Nagase ChemteX Corporation
- glycerin type epoxy resin epoxy equivalent 141, hydroxyl group equivalent 274 "Denacol” (registered trademark)
- EX-314 manufactured by Nagase ChemteX Corporation
- glycerin type epoxy resin epoxy equivalent 144, hydroxyl group equivalent 469
- Denacol registered trademark
- EX-321 trimethylolpropane type epoxy resin
- epoxy equivalent 140, hydroxyl equivalent 302 "Denacol” (registered trademark) EX-421 manufactured by Nagase ChemteX Corporation
- diglycerol type epoxy resin epoxy equivalent 159, hydroxyl group equivalent 435 "Denacol” (registered trademark) EX-614 (manufactured by Nagase ChemteX Corporation): diglycerol type epoxy resin, epoxy equivalent 159, hydroxyl group equivalent 435 "Denacol” (register
- Epoxy Resin “jER” (Registered Trademark) 1001 (Mitsubishi Chemical Corporation): Bisphenol A Type Epoxy Resin, Epoxy Equivalent 475, Hydroxyl Equivalent 449 "Epototo” (registered trademark) YD-128 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.): bisphenol A type epoxy resin, epoxy equivalent 189 "Epototo” (registered trademark) YDF-170 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.): bisphenol F type epoxy resin, epoxy equivalent 170 "Celoxide” (registered trademark) 2021P (manufactured by Daicel Corporation): alicyclic epoxy resin, epoxy equivalent 137
- Acid anhydride HN-5500 (manufactured by Hitachi Chemical Co., Ltd.): Methyl hexahydrophthalic acid anhydride, “Kayahard” (registered trademark) MCD (manufactured by Nippon Kayaku Co., Ltd.): Methyl nadic acid anhydride
- Curing accelerator triphenylphosphine “TPP” (manufactured by KAI Chemical Industries, Ltd.) ⁇ Tri-o-tolylphosphine “TOTP” (made by Hokuko Chemical Co., Ltd.) "CUREZOL” (registered trademark) 12DMZ (manufactured by Shikoku Chemicals Co., Ltd.): 1,2-dimethylimidazole
- ⁇ Preparation of epoxy resin composition An epoxy resin was blended at the blending ratio shown in Table 1 to obtain a main agent liquid. An acid anhydride and a curing accelerator were blended at a blending ratio shown in Table 1 to obtain a curing agent solution. Using these main agent liquid and curing agent liquid, an epoxy resin composition was prepared by blending at a blending ratio described in Table 1.
- the viscosity of the epoxy resin composition was measured in accordance with a measuring method using a conical plate type rotational viscometer in ISO 2884-1 (1994).
- a TVE-30H type manufactured by Toki Sangyo Co., Ltd. was used as the apparatus.
- the rotor was 1 ° 34 ′ ⁇ R24, and the sample amount was 1 cm 3 .
- the initial viscosity at 25 ° C. was measured immediately after the preparation of the epoxy resin composition.
- the viscosity A at 40 ° C. immediately after the preparation of the epoxy resin composition and the viscosity B at 40 ° C. after keeping the temperature at 40 ° C. for 20 minutes immediately after the preparation of the epoxy resin composition are measured.
- the value was calculated as the thickening factor N after 20 minutes at 40 ° C. of the composition, and used as an index of viscosity stability.
- Dielectric measurements were made to follow the curing behavior of the resin.
- an MDE-10 cure monitor manufactured by Holometrix-Micromet was used as a dielectric measurement device.
- a Viton O-ring with an inner diameter of 32 mm and a thickness of 3 mm is installed on the lower surface of the programmable mini press MP2000 with a TMS-1 inch type sensor embedded in the lower surface, the press temperature is set to 120 ° C, and epoxy resin is placed inside the O-ring.
- the composition was poured, the press was closed, and the time change of the ionic viscosity of the resin composition was followed.
- Dielectric measurement was performed at frequencies of 1, 10, 100, 1000, and 10000 Hz, and logarithm Log ( ⁇ ) of frequency independent ion viscosity was obtained using the attached software.
- Cure index ⁇ log ( ⁇ t) ⁇ log ( ⁇ min) ⁇ / ⁇ log ( ⁇ max) ⁇ log ( ⁇ min) ⁇ ⁇ 100 (Expression 5)
- ⁇ Preparation of cured resin plate> A copper spacer having a thickness of 2 mm, in which a square with a side of 50 mm was cut out, was placed on the lower surface of the press device, the press temperature was set to 120 ° C., the epoxy resin composition was poured inside the spacer, and the press was closed. After 20 minutes, the press was opened to obtain a cured resin plate.
- Tg of cured resin A test piece having a width of 12.7 mm and a length of 40 mm was cut out from the cured resin plate and subjected to torsional DMA measurement using a rheometer (ARES manufactured by TA Instruments). The measurement conditions were a heating rate of 5 ° C./min. The temperature at the inflection point of the storage elastic modulus G ′ obtained by the measurement was defined as Tg.
- Cavity carbon fiber fabric CO6343 (carbon fiber: T300-3K, organization: plain weave, basis weight: 198 g / m 2 , manufactured by Toray Industries, Inc.) as a reinforcing fiber in a mold having a plate-like cavity of 350 mm ⁇ 700 mm ⁇ 2 mm
- a mold having a plate-like cavity of 350 mm ⁇ 700 mm ⁇ 2 mm
- the main component of the epoxy resin composition in which the inside of the mold maintained at 100 ° C. (molding temperature) is depressurized to atmospheric pressure ⁇ 0.1 MPa by a vacuum pump and heated to 50 ° C. in advance.
- the liquid and the curing agent liquid were mixed using a resin injection machine and injected at a pressure of 0.2 MPa. Twenty minutes after the start of injection of the epoxy resin composition, the mold was opened and demolded to obtain a fiber-reinforced composite material.
- the void amount in the molded product is a value obtained by observing a smoothly polished cross section of the molded product with a falling oblique optical microscope and calculating the area ratio of voids in the molded product.
- Example 1 As described above, an epoxy resin composition was prepared, and viscosity measurement and dielectric measurement were performed. Further, using the prepared epoxy resin composition, a cured resin plate and a fiber-reinforced composite material were produced as described above.
- the epoxy resin composition of the present invention maintains a low-viscosity state with a low increase in viscosity even when held at a low temperature of 40 ° C.
- the demoldable time represented by t90 at 120 ° C. is short, it can be seen that the molding time of the fiber-reinforced composite material is also effective for shortening the molding time.
- the Tg of the cured resin exceeds the molding temperature (120 ° C.), it can be easily removed without deformation when the molded product is taken out from the mold.
- an epoxy resin composition outside the scope of the present invention has not obtained satisfactory characteristics.
- Comparative Example 1 since the component [A] is not included, the curing time is longer than in the Example, resulting in poor productivity during molding.
- Comparative Example 2 since the component [A] is more than the mass blending ratio 50:50 of the component [A] and the component [B], the viscosity at a low temperature of 40 ° C. is remarkably increased and the viscosity stability of the resin composition is inferior. This results in poor impregnation of reinforcing fibers.
- Comparative Example 3 since the component [B] is not included, in addition to the physical properties of Comparative Example 2, the heat resistance of the cured product is reduced.
- Comparative Example 4 As a result of adding an epoxy resin having a hydroxyl group equivalent of 500 or less but an epoxy equivalent of more than 250 instead of component [A], the viscosity of the resin composition was high, the viscosity increase ratio was high, and the viscosity was stable. Therefore, the impregnation property to the reinforcing fiber is inferior.
- Comparative Example 5 in which glycerin was added as a compound having a hydroxyl group instead of component [A], the viscosity increase at a low temperature of 40 ° C. was remarkably inferior in the viscosity stability of the resin composition.
- the epoxy resin composition of the present invention is suitable for forming a fiber reinforced composite material.
- the fiber reinforced excellent in appearance and surface quality.
- a composite material can be obtained with high productivity in a short time.
- the epoxy resin composition of the present invention is excellent in molding a fiber-reinforced composite material having a large shape, and is particularly suitable for application to automobile members.
- the epoxy resin composition of the present invention has excellent workability during resin preparation, excellent viscosity stability at low temperatures of the resin composition, cures in a short time during molding, and gives a high-grade fiber-reinforced composite material.
- a high-quality fiber-reinforced composite material can be provided with high productivity by the RTM method or the like.
- the application of fiber-reinforced composite materials for automobiles is especially advanced, and it can be expected to contribute to the improvement of fuel economy and the reduction of greenhouse gas emissions by further reducing the weight of automobiles.
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Abstract
Description
[A]エポキシ当量が250以下で、かつ水酸基当量が500以下のエポキシ樹脂
[B]成分[A]以外のエポキシ樹脂
[C]酸無水物
[D]有機リン化合物またはイミダゾール誘導体
[A]エポキシ当量が250以下で、かつ水酸基当量が500以下のエポキシ樹脂
[B]成分[A]以外のエポキシ樹脂
[C]酸無水物
[D]有機リン化合物またはイミダゾール誘導体
COH=(Σ(wn/wnOH))/W×1000 ・・・(式1)
COH:エポキシ樹脂組成物中の水酸基量(モル/kg)
wn:各成分の質量部
wnOH:各成分の水酸基当量(g/eq)
W:全成分の質量部の和
0.5≦t10≦4 ・・・・・(式2)
0.5≦t90≦9 ・・・・・(式3)
1<t90/t10≦2.5 ・・・(式4)
(ここで、t10は、温度T’における測定開始からキュアインデックスが10%に到達するまでの時間(分)を表し、t90は、測定開始からキュアインデックスが90%に到達する時間(分)を表す。)。
キュアインデックス={log(αt)-log(αmin)}/{log(αmax)-log(αmin)}×100 ・・・(式5)
キュアインデックス:(単位:%)
αt:時間tにおけるイオン粘度(単位:Ω・cm)
αmin:イオン粘度の最小値(単位:Ω・cm)
αmax:イオン粘度の最大値(単位:Ω・cm)。
Vf(%)=(Af×N)/(ρf×h)/10 ・・・(式6)
Af:繊維基材1枚・1m2当たりの質量(g/m2)
N:繊維基材の積層枚数(枚)
ρf:強化繊維の密度(g/cm3)
h:繊維強化複合材料(試験片)の厚み(mm)。
各実施例の樹脂組成物を得るために、以下の樹脂原料を用いた。なお、表1中の樹脂組成物の含有割合の単位は、特に断らない限り「質量部」を意味する。
・“デナコール”(登録商標)EX-313(ナガセケムテックス(株)製):グリセリン型エポキシ樹脂、エポキシ当量141、水酸基当量274
・“デナコール”(登録商標)EX-314(ナガセケムテックス(株)製):グリセリン型エポキシ樹脂、エポキシ当量144、水酸基当量469
・“デナコール”(登録商標)EX-321(ナガセケムテックス(株)製):トリメチロールプロパン型エポキシ樹脂、エポキシ当量140、水酸基当量302
・“デナコール”(登録商標)EX-421(ナガセケムテックス(株)製):ジグリセロール型エポキシ樹脂、エポキシ当量159、水酸基当量435
・“デナコール”(登録商標)EX-614(ナガセケムテックス(株)製):ソルビトール型エポキシ樹脂、エポキシ当量167、水酸基当量229
・“EPICLON”(登録商標)HP-820(DIC(株)製):水酸基のあるアルキルジフェノール型エポキシ樹脂、エポキシ当量220、水酸基当量490
・“jER”(登録商標)1001(三菱化学(株)製):ビスフェノールA型エポキシ樹脂、エポキシ当量475、水酸基当量449
・“エポトート”(登録商標)YD-128(新日鉄住金化学(株)製):ビスフェノールA型エポキシ樹脂、エポキシ当量189
・“エポトート”(登録商標)YDF-170(新日鉄住金化学(株)製):ビスフェノールF型エポキシ樹脂、エポキシ当量170
・“セロキサイド”(登録商標)2021P((株)ダイセル製):脂環式エポキシ樹脂、エポキシ当量137
・HN-5500(日立化成(株)製):メチルヘキサヒドロフタル酸無水物
・“カヤハード”(登録商標)MCD(日本化薬(株)製):メチルナジック酸無水物
・トリフェニルホスフィン「TPP」(ケイ・アイ化成(株)製)
・トリ-o-トリルホスフィン「TOTP」(北興化学(株)製)
・“キュアゾール”(登録商標)12DMZ(四国化成工業(株)製):1,2-ジメチルイミダゾール
・グリセリン(関東化学(株)製)
表1に記載した配合比でエポキシ樹脂を配合し主剤液とした。表1に記載した配合比で酸無水物、硬化促進剤を配合し硬化剤液とした。これら主剤液と硬化剤液とを用い、表1に記載した配合比で配合してエポキシ樹脂組成物を調製した。
ISO 2884-1(1994)における円錐平板型回転粘度計を使用した測定方法に準拠して、エポキシ樹脂組成物の粘度を測定した。装置には東機産業(株)製のTVE-30H型を用いた。ここでローターは1゜34’×R24を用い、サンプル量は1cm3とした。25℃の初期粘度は、エポキシ樹脂組成物の調製直後に測定した。また、エポキシ樹脂組成物の調製直後の40℃での粘度Aと、エポキシ樹脂組成物の調製直後から40℃20分保温後の40℃での粘度Bを測定し、BとAとの比の値を、組成物の40℃20分後増粘倍率Nとして算出し、粘度安定性の指標とした。
樹脂の硬化挙動を追跡するために誘電測定を行った。誘電測定装置として、Holometrix―Micromet社製のMDE-10キュアモニターを使用した。TMS-1インチ型センサーを下面に埋め込んだプログラマブルミニプレスMP2000の下面に内径32mm、厚さ3mmのバイトン製Oリングを設置し、プレスの温度を120℃に設定し、Oリングの内側にエポキシ樹脂組成物を注ぎ、プレスを閉じ、樹脂組成物のイオン粘度の時間変化を追跡した。誘電測定は1、10、100、1000、および10000Hzの各周波数で行い、付属のソフトウェアを用いて、周波数非依存のイオン粘度の対数Log(α)を得た。
キュアインデックス={log(αt)-log(αmin)}/{log(αmax)-log(αmin)}×100 ・・・(式5)
キュアインデックス:(単位:%)
αt:時間tにおけるイオン粘度(単位:Ω・cm)
αmin:イオン粘度の最小値(単位:Ω・cm)
αmax:イオン粘度の最大値(単位:Ω・cm)。
プレス装置下面に、一辺50mmの正方形をくり抜いた、厚さ2mmの銅製スペーサーを設置し、プレスの温度を120℃に設定し、エポキシ樹脂組成物をスペーサーの内側に注ぎ、プレスを閉じた。20分後にプレスを開け、樹脂硬化板を得た。
樹脂硬化板から幅12.7mm、長さ40mmの試験片を切り出し、レオメーター(TAインスツルメンツ社製ARES)を用いてねじりDMA測定を行った。測定条件は、昇温速度5℃/分とした。測定で得られた貯蔵弾性率G’の変曲点での温度をTgとした。
力学試験用の繊維強化複合材料としては、下記のRTM法によって作製したものを用いた。
上記のようにして繊維強化複合材料を作製する際の樹脂注入工程における含浸性について、以下の3段階で比較評価した。成形品中のボイド量が1%未満と、ボイドが実質的に存在しないものを“good”、成形品の外観に樹脂未含浸部分は認められないが、成形品中のボイド量が1%以上であるものを“fair”、成形品の外観に樹脂未含浸部分が認められるものを“bad”とした。
上記のようにして繊維強化複合材料を作製する際の脱型工程における作業性について、以下の3段階で比較評価した。金型を開き、成形品をスパチュラで金型から引き剥がす際、抵抗なく簡単に脱型されるものを“good”、抵抗はあるものの成形品が塑性変形することなく脱型できるもの(脱型作業に時間を要するため実用上は“good”に劣る)を“fair”、脱型困難もしくは脱型の際に成形品が塑性変形してしまうものを“bad”とした。
前記したようにして、エポキシ樹脂組成物を調製し、粘度測定、誘電測定を行った。また、調製したエポキシ樹脂組成物を用いて、前記したようにして樹脂硬化板、繊維強化複合材料を作製した。
前記したようにして、エポキシ樹脂組成物を調製し、粘度測定、誘電測定を行った。また、調製したエポキシ樹脂組成物を用いて、前記したようにして樹脂硬化板、繊維強化複合材料を作製した。
Claims (12)
- 次の[A]~[D]の成分を含み、かつ成分[A]と成分[B]の質量配合比が5:95~50:50である、繊維強化複合材料用2液型エポキシ樹脂組成物。
[A]エポキシ当量が250以下で、かつ水酸基当量が500以下のエポキシ樹脂
[B]成分[A]以外のエポキシ樹脂
[C]酸無水物
[D]有機リン化合物またはイミダゾール誘導体 - 成分[A]のエポキシ樹脂がエポキシ基を2個以上有する、請求項1に記載の繊維強化複合材料用2液型エポキシ樹脂組成物。
- 成分[A]がポリオールから誘導された脂肪族グリシジルエーテルである、請求項1または2に記載の繊維強化複合材料用2液型エポキシ樹脂組成物。
- 成分[A]がグリセリン型エポキシ樹脂、トリメチロールプロパン型エポキシ樹脂、ソルビトール型エポキシ樹脂から選ばれるエポキシ樹脂である、請求項1または2に記載の繊維強化複合材料用2液型エポキシ樹脂組成物。
- 成分[B]がビスフェノール型エポキシ樹脂である、請求項1~4のいずれかに記載の繊維強化複合材料用2液型エポキシ樹脂組成物。
- 成分[C]の酸無水物が脂環式構造を有する、請求項1~5のいずれかに記載の繊維強化複合材料用2液型エポキシ樹脂組成物。
- 樹脂組成物中の水酸基量が、エポキシ樹脂組成物1kg中のモルで表した場合、0.1モル/kg以上、1.0モル/kg以下である、請求項1~6のいずれかに記載の繊維強化複合材料用2液型エポキシ樹脂組成物。
- 樹脂組成物において、全成分混合直後から40℃20分保温後の粘度と、全成分混合直後の40℃における粘度との比の値をNとし、樹脂組成物を一定温度Tで保持した際の誘電測定で求められるキュアインデックスが、90%となる時間をt90(単位:分)としたとき、N×t90≦12を満たす特定温度Tを有する、請求項1~7のいずれかに記載の繊維強化複合材料用2液型エポキシ樹脂組成物。
- 25℃における粘度が0.1~2.5Pa・sである、請求項1~8のいずれかに記載の繊維強化複合材料用2液型エポキシ樹脂組成物。
- 成分[A]および[B]を含む主剤液と、成分[C]および[D]を含む硬化剤液とを混合してなる、請求項1~9のいずれかに記載の繊維強化複合材料用2液型エポキシ樹脂組成物。
- 請求項1~10のいずれかに記載の繊維強化複合材料用2液型エポキシ樹脂組成物と強化繊維を組み合わせ、硬化してなる、繊維強化複合材料。
- 強化繊維が炭素繊維である、請求項11記載の繊維強化複合材料。
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WO2017221542A1 (ja) * | 2016-06-24 | 2017-12-28 | 東レ株式会社 | 繊維強化複合材料用2液型エポキシ樹脂組成物および繊維強化複合材料 |
JP6658986B1 (ja) * | 2018-09-10 | 2020-03-04 | 東レ株式会社 | エポキシ樹脂組成物、繊維強化複合材料用成形材料および繊維強化複合材料 |
JP2020063438A (ja) * | 2018-10-11 | 2020-04-23 | 三菱ケミカル株式会社 | 樹脂組成物、樹脂硬化物および複合成形体 |
WO2020110528A1 (ja) * | 2018-11-29 | 2020-06-04 | Dic株式会社 | 2液硬化型エポキシ樹脂組成物、硬化物、繊維強化複合材料及び成形品 |
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WO2019065470A1 (ja) * | 2017-09-29 | 2019-04-04 | 日鉄ケミカル&マテリアル株式会社 | 硬化性エポキシ樹脂組成物、及びそれを用いた繊維強化複合材料 |
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US20160237273A1 (en) | 2016-08-18 |
KR20160065870A (ko) | 2016-06-09 |
EP3053941A4 (en) | 2017-05-10 |
CN105593261A (zh) | 2016-05-18 |
EP3053941A1 (en) | 2016-08-10 |
JPWO2015046030A1 (ja) | 2017-03-09 |
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