WO2015146504A1 - エポキシ樹脂、エポキシ樹脂の製造方法、硬化性樹脂組成物、その硬化物、繊維強化複合材料、及び成形品 - Google Patents
エポキシ樹脂、エポキシ樹脂の製造方法、硬化性樹脂組成物、その硬化物、繊維強化複合材料、及び成形品 Download PDFInfo
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- PTQLCOGXXZWICB-UHFFFAOYSA-N C[N](c(cc1)ccc1OCC1OC1)(c1ccccc1OCC1OC1)c1ccccc1OCC1OC1 Chemical compound C[N](c(cc1)ccc1OCC1OC1)(c1ccccc1OCC1OC1)c1ccccc1OCC1OC1 PTQLCOGXXZWICB-UHFFFAOYSA-N 0.000 description 1
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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
- C08G59/20—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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- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
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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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
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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
- C08G59/20—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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- 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
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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
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
- C08G59/58—Amines together with other curing agents with polycarboxylic acids or with 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
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
- C08G59/60—Amines together with other curing agents with amides
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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
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
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- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
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- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/02—Polyglycidyl ethers of bis-phenols
Definitions
- the present invention is an epoxy resin having a low viscosity, excellent impregnation into reinforcing fibers, a high elastic modulus in a cured product when used in a fiber reinforced resin material, and excellent heat resistance, a method for producing the same, and curability
- the present invention relates to a resin composition, a cured product thereof, a fiber-reinforced composite material, and a molded product.
- Fiber reinforced composite materials are attracting attention because of their light weight and excellent heat resistance and mechanical strength, and their use in various structural applications such as automobile and aircraft casings and various members is expanding.
- the matrix resin of the fiber reinforced composite material has high impregnation into the reinforced fiber, excellent storage stability, high curability but no generation of voids, heat resistance in cured products, machinery
- There are various required performances such as excellent strength and fracture toughness, and there is a demand for the development of resin materials that are excellent in a balance between these various performances.
- a ratio of a peak (a) meaning an ortho-oriented skeleton in 13 C-NMR measurement to a peak (b) meaning a para-oriented skeleton is 0.25.
- An epoxy resin composition containing a trisphenol methane type epoxy resin of ⁇ 0.27 and a curing agent is disclosed (Patent Document 1).
- Patent Document 1 An epoxy resin composition containing a trisphenol methane type epoxy resin of ⁇ 0.27 and a curing agent.
- such a curable composition tends to deteriorate the impregnation property to the substrate due to an increase in viscosity, and in addition, a sufficient elastic modulus cannot be obtained in the cured product.
- the problem to be solved by the present invention is an epoxy having a low viscosity and excellent impregnation into reinforcing fibers, a high elastic modulus in a cured product when used in a fiber reinforced resin material, and excellent heat resistance. It is in providing a resin and its manufacturing method, a curable resin composition, its hardened
- the viscosity is low, the impregnation property to the reinforcing fiber is excellent, and the fiber reinforced resin material was used.
- the present inventors have found that an epoxy resin having a high elastic modulus in the cured product at the time and having excellent heat resistance is obtained, and the present invention has been completed.
- the present invention is a polyglycidyl ether of a polycondensate of phenol and hydroxybenzaldehyde, which has the following structural formula (1)
- the epoxy resin is characterized in that the content of the [o, p, p] conjugate (x1) represented by the formula is in the range of 5 to 18% in terms of area ratio in liquid chromatographic measurement.
- the present invention further provides a phenol resin intermediate by reacting phenol and orthohydroxybenzaldehyde at a molar ratio [(phenol) :( hydroxybenzaldehyde)] of 1: 0.05 to 1: 0.25. Then, the present invention relates to a method for producing an epoxy resin, characterized by reacting the obtained phenolic resin intermediate with epichlorohydrin.
- the present invention further relates to a curable resin composition containing the epoxy resin and a curing agent.
- the present invention further relates to a cured product obtained by curing the curable resin composition.
- the present invention further relates to a fiber-reinforced composite material containing the epoxy resin, a curing agent, and reinforcing fibers.
- the present invention further relates to a molded product obtained by curing the fiber-reinforced composite material.
- an epoxy resin having a low viscosity and excellent impregnation into a reinforcing fiber, a high elastic modulus in a cured product when used in a fiber reinforced resin material, and an excellent heat resistance and a production method thereof,
- a curable resin composition, a cured product thereof, a fiber-reinforced composite material, and a molded product can be provided.
- FIG. 1 is a GPC chart of the epoxy resin (1) obtained in Example 1.
- FIG. 2 is an HPLC chart of the epoxy resin (1) obtained in Example 1.
- FIG. 3 is a GPC chart of the epoxy resin (2) obtained in Example 2.
- FIG. 4 is an HPLC chart of the epoxy resin (2) obtained in Example 2.
- FIG. 5 is a GPC chart of the epoxy resin (1 ′) obtained in Comparative Production Example 1.
- FIG. 6 is an HPLC chart of the epoxy resin (1 ′) obtained in Comparative Production Example 1.
- the epoxy resin of the present invention is a polyglycidyl ether of a polycondensate of phenol and hydroxybenzaldehyde, and has the following structural formula (1)
- the content of the [o, p, p] conjugate (x1) represented by the formula is characterized in that the area ratio in the liquid chromatographic measurement is in the range of 5 to 18%.
- the trinuclear body (X) obtained by polyglycidyl etherification of a polycondensation product of phenol and hydroxybenzaldehyde is an [o, p, p] conjugate (x1) represented by the structural formula (1-1). ) And the following structural formulas (1-2) to (1-4)
- the distance between bonding points that is, the distance between epoxy groups in the compound is relatively long, so that an epoxy resin containing a large amount of these tends to have a reduced elastic modulus and a higher viscosity in the cured product.
- the glass transition temperature of the cured product is lowered and the heat resistance is lowered.
- the content of the [o, p, p] conjugate (x1) represented by the structural formula (1-1) in the trinuclear body (X) is 5 to 5 by area ratio in the liquid chromatographic measurement. By defining it in the range of 18%, a cured product having low viscosity and excellent in both heat resistance and elastic modulus can be obtained.
- the content rate of each component in the said trinuclear body (X) measured by the liquid chromatograph measurement by the above is a value calculated from the area ratio of the liquid chromatograph (HPLC) chart figure measured on condition of the following. is there.
- the [o, o, p] conjugate (x2) represented by the structural formula (1-2) is a compound having an excellent balance between the distance between bond points and the density. Therefore, the epoxy resin of the present invention preferably contains the [o, o, p] conjugate (x2).
- the content of the [o, o, p] conjugate (x2) in the trinuclear body (X) is determined in liquid chromatographic measurement.
- the area ratio is preferably in the range of 53 to 60%.
- the epoxy resin of the present invention is polyglycidyl ether which is a polycondensate of phenol and hydroxybenzaldehyde. Especially, since it is easy to adjust content of the said [o, p, p] conjugate
- the trinuclear body (X) includes the [o, p, p] conjugate (x1), the [o, o, p] conjugate (x2), and the [o, o, o] conjugate ( x3).
- the content of each component in the trinuclear body (X) is excellent in heat resistance and a cured product having a high elastic modulus is obtained, the above [o] when the total of these three components is 100%.
- P, p] conjugate (x1) content is in the range of 5-18%
- the [o, o, p] conjugate (x2) content is in the range of 53-60%
- the content of the [o, o, o] conjugate (x3) is preferably in the range of 28 to 40%.
- the epoxy resin of the present invention has a low viscosity and excellent impregnation into reinforcing fibers by using the trinuclear body (X) as an essential component. Especially, since it is further excellent in the impregnation property to a reinforced fiber, it is preferable that content of the said trinuclear body (X) in an epoxy resin is 70% or more in the area ratio in GPC measurement.
- the content of the trinuclear body (X) in the epoxy resin is a value calculated from the area ratio of the GPC chart measured under the following conditions.
- Measuring device “HLC-8220 GPC” manufactured by Tosoh Corporation Column: Guard column “HXL-L” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + Tosoh Corporation “TSK-GEL G3000HXL” + “TSK-GEL G4000HXL” manufactured by Tosoh Corporation Detector: RI (differential refractometer) Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation Measurement conditions: Column temperature 40 ° C Developing solvent Tetrahydrofuran Flow rate 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used according toso
- the epoxy equivalent of the epoxy resin of the present invention is preferably in the range of 160 to 170 g / equivalent because it is excellent in both the heat resistance in the cured product and the impregnation into the reinforcing fiber.
- the epoxy resin of the present invention is obtained by polyglycidyl etherification of a polycondensate of phenol and hydroxybenzaldehyde using epichlorohydrin or the like, and its production method is not particularly limited.
- the reaction between phenol and hydroxybenzaldehyde can be carried out, for example, with phenolhydroxybenzaldehyde in the presence of an acid catalyst at a temperature of 100 to 130 ° C.
- the reaction ratio between phenol and hydroxybenzaldehyde is usually set to a condition that 1 mol or less of hydroxybenzaldehyde per 1 mol of phenol.
- the molar ratio [(phenol) :( hydroxybenzaldehyde)] of the both is more preferably in the range of 1: 0.05 to 1: 0.25, whereby the trinuclear body in the epoxy resin is obtained. It becomes easy to adjust the content of (X) and the content of each component in the trinuclear body (X) to the preferred values.
- Examples of the acid catalyst used for the reaction between phenol and hydroxybenzaldehyde include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, boron trifluoride, Examples include Lewis acids such as anhydrous aluminum chloride and zinc chloride. These may be used alone or in combination of two or more. Among these, paratoluenesulfonic acid is preferable because of its high reaction promoting ability.
- the amount of the acid catalyst used is preferably in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass in total of phenol and hydroxybenzaldehyde because the reaction proceeds efficiently.
- the reaction between phenol and hydroxybenzaldehyde may be performed in an organic solvent as necessary.
- the organic solvent used here is not particularly limited as long as it is an organic solvent that can be used under the above temperature conditions. Specific examples include methyl cellosolve, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. . When these organic solvents are used, they are preferably used in the range of 10 to 500 parts by mass with respect to 100 parts by mass of the total of antiphenol and hydroxybenzaldehyde.
- reaction mixture is neutralized with a basic substance such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, triethylenetetramine, aniline, and excess phenol is removed by an operation such as steam distillation.
- a basic substance such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, triethylenetetramine, aniline, and excess phenol is removed by an operation such as steam distillation.
- a phenolic resin intermediate is obtained.
- epihalohydrin is added in a range of 2 to 10 moles with respect to 1 mole of hydroxyl group in the phenol resin intermediate, and further in the phenol resin intermediate.
- Examples include a method of reacting at a temperature of 20 to 120 ° C. for 0.5 to 10 hours while adding or gradually adding 0.9 to 2.0 mol of a basic catalyst with respect to 1 mol of a hydroxyl group.
- epihalohydrin examples include epichlorohydrin, epibromohydrin, ⁇ -methylepichlorohydrin, and the like. These may be used alone or in combination of two or more. Of these, epichlorohydrin is preferred because it is easily available industrially.
- all of the epihalohydrins used for preparation are new in industrial production, but the following batch and subsequent batches react with epihalohydrin recovered from the crude reaction product produced in the manufacturing process. It is preferable to use together with a new epihalohydrin corresponding to the amount consumed by the amount consumed.
- the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides.
- alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity of the epoxy resin synthesis reaction, and examples thereof include sodium hydroxide and potassium hydroxide.
- these basic catalysts may be used in the form of an aqueous solution of about 10 to 55% by mass, or in the form of a solid.
- a basic catalyst is continuously added to the reaction system, and water and epihalohydrin are continuously distilled from the reaction mixture under reduced pressure or atmospheric pressure conditions. The water is removed and the epihalohydrin is continuously returned to the reaction mixture.
- the reaction between the phenol resin intermediate and epihalohydrin is carried out in an organic solvent to increase the reaction rate, and the target epoxy resin can be produced efficiently.
- the organic solvent used here is not particularly limited.
- ketones such as acetone and methyl ethyl ketone
- alcohol compounds such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, and tertiary butanol
- methyl cellosolve And cellosolves such as ethyl cellosolve
- ether compounds such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane
- aprotic polar solvents such as acetonitrile, dimethyl sulfoxide and dimethylformamide.
- the reaction product is washed with water, and unreacted epihalohydrin and the combined organic solvent are distilled off under heating and reduced pressure conditions. Furthermore, in order to further reduce hydrolyzable halogen in the resulting epoxy resin, the epoxy resin is dissolved again in an organic solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, and alkali metal water such as sodium hydroxide and potassium hydroxide. Further reaction can be carried out by adding an aqueous solution of oxide. At this time, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present for the purpose of improving the reaction rate.
- an organic solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, and alkali metal water such as sodium hydroxide and potassium hydroxide.
- Further reaction can be carried out by adding an aqueous solution of oxide.
- a phase transfer catalyst such as a qua
- the amount used is preferably 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the epoxy resin used.
- the melt viscosity at 150 ° C. is preferably in the range of 1 to 100 mPa ⁇ s, more preferably in the range of 1 to 90 mPa ⁇ s. preferable.
- the curable resin composition of the present invention contains the epoxy resin of the present invention and a curing agent.
- Examples of the curing agent used here include amine compounds, amide compounds, acid anhydrides, phenol resins, and the like. These may be used alone or in combination of two or more.
- Examples of the amine compounds include dicyandiamide compounds, aromatic amine compounds, diethylenetriamine, triethylenetetramine, isophoronediamine, imidazole, BF 3 -amine complexes, guanidine derivatives, and the like.
- the amide compound include polyamide resin synthesized from dimer of dicyandiamide and linolenic acid and ethylenediamine.
- Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydro And phthalic anhydride.
- Examples of the phenol resin include phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, dicyclopentadiene phenol addition type resins, phenol aralkyl resins (Zylok resins), and polyvalent resins represented by resorcin novolac resins.
- an acid anhydride when it is desired to obtain a curable resin composition having low viscosity and excellent storage stability, it is preferable to use an acid anhydride, and among them, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl anhydride It is more preferable to use alicyclic acid anhydrides such as nadic acid, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.
- the blending ratio of the epoxy resin component and the curing agent is excellent in curability, has a high elastic modulus and is excellent in heat resistance, so that a total of 1 equivalent of epoxy groups in the epoxy resin component is obtained.
- the amount is preferably such that the active group in the curing agent is 0.5 to 1.5 equivalents.
- the curability is low viscosity
- the cured product has a high modulus of elasticity, excellent heat resistance, and does not deteriorate even when exposed to wet heat conditions, and can maintain high performance.
- a dicyandiamide compound used as a curing agent for the epoxy resin is a compound obtained by modifying a functional group in dicyandiamide or dicyandiamide, that is, an amino group, an imino group, or a cyano group.
- o-tolyl biguanide, diphenyl biguanide, etc. Is mentioned. These may be used alone or in combination of two or more.
- the blending ratio of the epoxy resin component and the dicyandiamide compound is excellent in curability, has a high elastic modulus and is excellent in heat resistance, so that a total of 1 equivalent of epoxy groups in the epoxy resin component is obtained.
- the molar ratio of active hydrogen in the dicyandiamide compound is preferably 0.5 to 1.0 equivalent.
- an aromatic amine compound used as a curing agent for the epoxy resin is not particularly limited as long as it is an aromatic amine, but is preferably a compound having a plurality of aromatic rings to which amino groups are directly bonded.
- the blending ratio of the epoxy resin component and the aromatic amine compound is excellent in curability, and a cured product having excellent heat resistance and high elastic modulus can be obtained. It is preferable that the number of moles of active hydrogen in the aromatic amine compound is 0.7 to 1.3 equivalents with respect to a total of 1 equivalent of epoxy groups in the epoxy resin contained in the curable resin component.
- the curable resin composition of the present invention may use other epoxy resins other than the epoxy resin of the present invention as an epoxy resin component.
- the epoxy resin of the present invention can be used in combination with other epoxy resins in an amount of 30% by mass or more, preferably 40% by mass or more with respect to the total mass of the epoxy resin component.
- epoxy resins can be used as the other epoxy resins, for example, bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins; biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, etc. Biphenyl type epoxy resins; phenol novolak type epoxy resins, cresol novolak type epoxy resins, naphthol novolak type epoxy resins, naphthol-phenol co-condensed novolak type epoxy resins, bisphenol A novolak type epoxy resins, biphenyl novolak type epoxy resins, etc.
- bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins
- biphenyl type epoxy resins tetramethylbiphenyl type epoxy resins, etc.
- Biphenyl type epoxy resins phenol novolak type epoxy resins, cresol novolak type epoxy resins, naphthol novolak type epoxy resins, naphthol-phenol co-con
- Aralkyl epoxy resins such as phenol aralkyl epoxy resins and naphthol aralkyl epoxy resins
- Tetraphenylethane epoxy resins Dicyclopentadiene - phenol addition reaction type epoxy resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resins.
- a bisphenol type epoxy resin is preferable because a cured product having a high elastic modulus can be obtained.
- the curable resin composition of the present invention may contain various additives such as a curing accelerator and a flame retardant as necessary.
- Examples of the curing accelerator include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, and the like.
- examples of the curing accelerator include 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2 -Imidazole compounds such as ethyl-2-phenylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; tertiary amine compounds such as triethylamine and 2,4,6-tris (dimethylaminomethyl) phenol, trifluoride Lewis acid complexes such as boron halides such as boron / piperidine complex, boron trifluoride / monoethylamine complex, boron trifluoride / triethanolamine complex, boron halides such as boron / piperidine complex, boron tri
- the flame retardant is, for example, red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphate such as ammonium polyphosphate, inorganic phosphorus compounds such as phosphate amide; phosphate ester compound, phosphonic acid Compound, phosphinic acid compound, phosphine oxide compound, phosphorane compound, organic nitrogen-containing phosphorus compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxyphenyl) ) Cyclic organic phosphorus such as -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7-dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide Compound and its compound such as epoxy resin and phenol resin Organophosphorus compounds such as derivatives reacted with nitrogen; nitrogen
- the curable resin composition of the present invention may contain a thermoplastic resin as necessary. Although it does not specifically limit as a thermoplastic resin, The thermoplastic resin which is soluble in an epoxy resin and has a hydrogen bondable functional group is preferable. When the curable resin composition of the present invention contains the thermoplastic resin as described above, the epoxy resin and the thermoplastic resin are combined with each other, and the adhesion between the reinforcing fiber and the curable resin composition is improved.
- thermoplastic resin having a hydrogen bondable functional group examples include thermoplastic resins having a functional group such as a hydroxyl group, an amide bond, and a sulfonyl group.
- thermoplastic resin having a hydroxyl group examples include polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, polyvinyl alcohol, and phenoxy resins.
- thermoplastic resin having an amide bond examples include polyamide, polyimide, and polyvinyl pyrrolidone.
- thermoplastic resin having a sulfonyl group examples include polysulfone.
- polyamide, polyimide, and polysulfone may have a functional group such as an ether bond or a carbonyl group in the main chain. Furthermore, among the above, the polyamide may have a substituent on the nitrogen atom of the amide group.
- thermoplastic resin described above can be produced by a known method, but it is easy to use a commercially available product.
- commercially available thermoplastic resins include polyvinyl acetal resins such as Denkabutyral and “Denka Formal (registered trademark)” (manufactured by Denki Kagaku Kogyo Co., Ltd.), “Vinylec (registered trademark)” ( Chisso Co., Ltd.) as phenoxy resin, for example, “UCAR (registered trademark)” PKHP (manufactured by Union Carbide), and polyamide resin, for example, “Macromelt (registered trademark)” (manufactured by Henkel Hakusui Co., Ltd.) ), “Amilan (registered trademark)” CM4000 (manufactured by Toray Industries, Inc.), for example, “Ultem (registered trademark)” (manufactured by General Electric), “Matrimid
- the curable resin composition of the present invention can also contain thermoplastic resins other than those described above.
- thermoplastic resin include acrylic resins.
- the acrylic resin is soluble in the epoxy resin and highly compatible with the epoxy resin. Therefore, it is suitable for controlling the viscoelasticity of the curable resin composition.
- commercially available acrylic resins include “Dianal (registered trademark)” BR series (manufactured by Mitsubishi Rayon Co., Ltd.), “Matsumoto Microsphere (registered trademark)” M, M100, M500 (Matsumoto Yushi Seiyaku ( Product)).
- the curable resin composition of the present invention may contain other additives as necessary.
- other additives include organic and inorganic particles.
- examples of the organic and inorganic particles include rubber particles and thermoplastic resin particles.
- the rubber particles are not particularly limited, but for example, cross-linked rubber particles and core-shell rubber particles obtained by graft polymerization of a different polymer on the surface of the cross-linked rubber particles are preferable from the viewpoint of handleability and the like.
- crosslinked rubber particles examples include FX501P (manufactured by Nippon Synthetic Rubber Industry) made of a crosslinked product of a carboxyl-modified butadiene-acrylonitrile copolymer, CX-MN series (made by Nippon Shokubai Co., Ltd.) made of acrylic rubber fine particles, And YR-500 series (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
- FX501P manufactured by Nippon Synthetic Rubber Industry
- CX-MN series made by Nippon Shokubai Co., Ltd.
- YR-500 series manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
- Examples of the core-shell rubber particles include “Paraloid (registered trademark)” EXL-2655 (manufactured by Kureha Chemical Co., Ltd.), an acrylate ester / methacrylate ester copolymer made of a butadiene / alkyl methacrylate / styrene copolymer.
- STAPHYLOID registered trademark
- TR-2122 manufactured by Takeda Pharmaceutical Co., Ltd.
- PARALOID registered trademark
- EXL-2611 composed of a butyl acrylate / methyl methacrylate copolymer
- Examples include EXL-3387 (manufactured by Rohm & Haas), “Kane Ace (registered trademark)” MX series (manufactured by Kaneka Corporation), and the like.
- thermoplastic resin particles for example, polyamide particles and polyimide particles are preferable.
- polyamide particles include SP-500 (manufactured by Toray Industries, Inc.), “Orgasol (registered trademark)” (manufactured by Arkema), and the like.
- the blending amount of organic particles such as rubber particles and thermoplastic resin particles is 0.1 when the total mass of the curable resin composition is 100 parts by mass from the viewpoint of achieving both the elastic modulus and toughness of the resulting cured product. It is preferably contained in a proportion of from 30 to 30 parts by mass, and more preferably contained in a proportion of from 1 to 15 parts by mass.
- the curable resin composition of the present invention is excellent in fluidity, has a high elastic modulus in a cured product, and can be used for various applications by taking advantage of excellent heat resistance.
- fiber reinforced resin molded products such as CFRP represented by automobile and aircraft casings and various members, laminated boards for printed wiring boards, interlayer insulating materials for build-up boards, adhesive films for build-up, semiconductor encapsulation Used for electronic circuit boards such as fixing materials, die attach agents, flip-chip mounting underfill materials, grab top materials, TCP liquid sealing materials, conductive adhesives, liquid crystal seal materials, flexible substrate coverlays, resist inks, etc.
- Resin materials such as optical waveguides and optical films, resin casting materials, adhesives, coating materials such as insulating paints, etc .; LED, phototransistor, photodiode, photocoupler, CCD, EPROM, photosensor, etc.
- Optical semiconductor devices, etc. It can be suitably used in the fiber-reinforced resin molded article applications CFRP or the like.
- an organic solvent may be appropriately blended as necessary.
- the organic solvent used here include acetone, methyl ethyl ketone, and ethyl acetate. Among them, it is preferable to use an organic solvent having a boiling point of 100 ° C. or lower. The amount of these organic solvents used depends on the intended application, but the amount of the organic solvent in the curable resin composition is preferably 60% by mass or less.
- the curable resin composition of the present invention is used for a fiber reinforced composite material, it is preferable not to use a substantial organic solvent.
- the amount of organic solvent in the fiber reinforced composite material is 5 It is preferable that it is below mass%.
- the organic solvent used here include acetone, methyl ethyl ketone, and ethyl acetate. Among them, it is preferable to use an organic solvent having a boiling point of 100 ° C. or lower.
- the reinforcing fiber used in the fiber-reinforced composite material of the present invention may be any of a twisted yarn, an untwisted yarn, or a non-twisted yarn, but an untwisted yarn or a non-twisted yarn is preferable because both the moldability and mechanical strength of the fiber-reinforced plastic member are compatible.
- the form of the reinforcing fiber can be a fiber in which the fiber directions are aligned in one direction or a woven fabric, and the woven fabric can be freely selected according to the part to be used and the application, such as plain weave and satin weave.
- Specific examples of the material include carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, and silicon carbide fiber because of excellent mechanical strength and durability.
- carbon fiber is preferable from the viewpoint that the strength of the molded product is particularly good.
- various types such as polyacrylonitrile-based, pitch-based, and rayon-based can be used.
- a polyacrylonitrile-based one that can easily obtain a high-strength carbon fiber is preferable.
- an organic solvent is used to prepare a varnish in which each component constituting the curable resin composition is uniformly mixed, and then the varnish is made from the reinforced fiber. After impregnating the resulting sheet-like fiber, the organic solvent is evaporated using an oven, etc. to make a fiber reinforced composite material, or the viscosity is reduced by heating without using an organic solvent on roll paper or release paper.
- a sheet on which the curable resin composition is laminated is manufactured, and then the surface of the sheet on which the curable resin composition is laminated is superimposed on both sides or one side of the sheet-like fiber made of reinforcing fibers, and heated and pressurized.
- a hot melt method for impregnation can be used as appropriate, it is preferable to use a hot melt method in which substantially no organic solvent remains in the fiber-reinforced composite material.
- the temperature reached by the curable resin composition in the impregnation step is 50 ° C. to 250 ° C.
- the range of 0 ° C. is preferable, and it is particularly preferable to pre-cure at 50 ° C. to 100 ° C. Since the ultimate temperature is 100 ° C. or lower, it is possible to suppress the glass transition temperature from rising due to partial progress of the curing reaction in the curable resin composition. Drapability can be maintained.
- the ultimate temperature is 50 ° C. or higher, the reinforcing fibers are sufficiently impregnated.
- the curable resin composition is not necessarily impregnated into the fiber bundle, and the curable resin composition is localized near the surface of the sheet-like fiber. An aspect may be sufficient.
- the volume content of the reinforced fiber with respect to the total volume of the fiber reinforced composite material is preferably 40% to 85%, and in the range of 50% to 70% from the viewpoint of strength. It is particularly preferred.
- the volume content is 40% or more, the cured product obtained from the fiber-reinforced composite material is excellent in flame retardancy.
- the volume content is 85% or less, the adhesion between the reinforced fiber and the curable resin composition is excellent, and when a plurality of fiber reinforced composite materials are laminated, the fiber reinforced composite materials are well bonded.
- a method for producing a fiber reinforced resin molded article using the fiber reinforced composite material of the present invention includes a hand lay-up method or a spray-up method in which a fiber aggregate is laid on a mold and the varnishes are laminated in layers, and Using one of the molds, a base made of reinforcing fibers is impregnated with a curable resin composition and then molded, covered with a flexible mold that can apply pressure to the molded product, and hermetically sealed.
- the fiber reinforced resin molded product produced by the method as described above preferably has a volume content of reinforcing fibers in the fiber reinforced molded product in the range of 40% to 85%, from the viewpoint of strength. A range of 50% to 70% is particularly preferable.
- Fiber-reinforced resin molded article thus obtained include sporting goods such as fishing rods, golf shafts, bicycle frames, automobiles, aircraft frames or body materials, spacecraft components, wind power generator blades, front subframes. , Rear subframes, front pillars, center pillars, side members, cross members, side sills, roof rails, propeller shafts and other automotive parts, core members for cable cables, pipe materials for subsea oil fields, roll and pipe materials for printing presses, robots Fork materials and the like can be mentioned, but in particular, high fracture toughness and mechanical strength are required for automobile members, aircraft members, and spacecraft members. Therefore, the fiber reinforced resin molded product of the present invention should be applied to these uses. Is preferred.
- the curable resin composition of the present invention can also be used as a cured product for applications other than the above applications.
- a method of obtaining a cured product from the curable resin composition of the present invention it is sufficient to comply with a general curing method of a curable resin composition.
- the heating temperature condition depends on the type and use of the curing agent to be combined. What is necessary is just to select suitably.
- a method in which the curable resin composition is heated in a temperature range of room temperature to about 250 ° C.
- a general method of a curable resin can be used, and a condition specific to the curable resin composition of the present invention is not particularly necessary.
- the content of each component in the trinuclear body (X) was calculated from the area ratio of a liquid chromatograph (HPLC) chart diagram measured under the following conditions.
- the melt viscosity of the epoxy resin was measured with an ICI viscometer in accordance with ASTM D4287.
- the softening point of the epoxy resin was measured according to IS K7234.
- Example 1 Production of Epoxy Resin (1) A flask equipped with a nitrogen introduction tube, a cooling tube, a thermometer, a Dean-Stark device and a stirrer was charged with 1128 g (12.0 mol) of phenol, 122 g (1.0 mol) of salicylaldehyde, para 12.5 g of toluenesulfonic acid was added, and the temperature was raised to 120 ° C. over 45 minutes with stirring. The condensed water produced by the reaction was reacted at 120 ° C. for 3 hours while distilling off with a Dean-Stark apparatus. After completion of the reaction, 5.1 g of 49% aqueous sodium hydroxide solution was added for neutralization, and the temperature was raised to 180 ° C.
- Normal temperature solid epoxy resin (2) was obtained in the same manner as in Production Example 1 except that 98 g (1.0 mol) of phenol resin intermediate (1) was changed to 98 g (1.0 mol) of phenol resin intermediate (2). It was.
- the GPC chart of the epoxy resin (2) is shown in FIG. 3, and the HPLC chart is shown in FIG.
- Epoxy resin (2) had an epoxy equivalent of 166 g / eq, a melt viscosity at 150 ° C. of 0.6 dPa ⁇ s, and a softening point of 56 ° C.
- the content of trinuclear (X) in the epoxy resin (2) calculated from the GPC chart is 56.9%, and [o, p in the trinuclear (X) calculated from the HPLC chart is calculated.
- the content was 39.4%.
- the content of trinuclear (X) in the epoxy resin (1 ′) calculated from the GPC chart is 65.8%, and [o, The content of the p, p] conjugate (x1) is 20.2%, and the content of the [o, o, p] conjugate (x2) is 52.1% [o, o, o] conjugate (x3) The content of was 27.7%.
- Table 1 The results are shown in Table 1.
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Abstract
Description
本発明のエポキシ樹脂は、フェノールとヒドロキシベンズアルデヒドとの重縮合物のポリグリシジルエーテルであって、下記構造式(1)
東ソー株式会社製「Agilent 1220 Infinity LC」、
カラム: 東ソー株式会社製「TSK-GEL ODS-120T」
検出器: VWD
データ処理:東ソー株式会社製「Agilent EZChrom Elite」
測定条件: カラム温度 40℃
展開溶媒 A液:水/アセトニトリル=50/50wt%
B液:アセトニトリル
展開条件 A液/B液=95/5(15min)
リニアグラジエント(20min)
A液/B液=0/100(20min)
流速 1.0ml/min
測定波長 254nm
測定装置 :東ソー株式会社製「HLC-8220 GPC」、
カラム:東ソー株式会社製ガードカラム「HXL-L」
+東ソー株式会社製「TSK-GEL G2000HXL」
+東ソー株式会社製「TSK-GEL G2000HXL」
+東ソー株式会社製「TSK-GEL G3000HXL」
+東ソー株式会社製「TSK-GEL G4000HXL」
検出器: RI(示差屈折計)
データ処理:東ソー株式会社製「GPC-8020モデルIIバージョン4.10」
測定条件: カラム温度 40℃
展開溶媒 テトラヒドロフラン
流速 1.0ml/分
標準 : 前記「GPC-8020モデルIIバージョン4.10」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
(使用ポリスチレン)
東ソー株式会社製「A-500」
東ソー株式会社製「A-1000」
東ソー株式会社製「A-2500」
東ソー株式会社製「A-5000」
東ソー株式会社製「F-1」
東ソー株式会社製「F-2」
東ソー株式会社製「F-4」
東ソー株式会社製「F-10」
東ソー株式会社製「F-20」
東ソー株式会社製「F-40」
東ソー株式会社製「F-80」
東ソー株式会社製「F-128」
試料 : 樹脂固形分換算で1.0質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの(50μl)
東ソー株式会社製「Agilent 1220 Infinity LC」、
カラム: 東ソー株式会社製「TSK-GEL ODS-120T」
検出器: VWD
データ処理:東ソー株式会社製「Agilent EZChrom Elite」
測定条件: カラム温度 40℃
展開溶媒 A液:水/アセトニトリル=50/50wt%
B液:アセトニトリル
展開条件 A液/B液=95/5(15min)
リニアグラジエント(20min)
A液/B液=0/100(20min)
流速 1.0ml/min
測定波長 254nm
標準 : 前記「GPC-8020モデルIIバージョン4.10」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
(使用ポリスチレン)
東ソー株式会社製「A-500」
東ソー株式会社製「A-1000」
東ソー株式会社製「A-2500」
東ソー株式会社製「A-5000」
東ソー株式会社製「F-1」
東ソー株式会社製「F-2」
東ソー株式会社製「F-4」
東ソー株式会社製「F-10」
東ソー株式会社製「F-20」
東ソー株式会社製「F-40」
東ソー株式会社製「F-80」
東ソー株式会社製「F-128」
試料 : 樹脂固形分換算で1.0質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの(50μl)
窒素導入管、冷却管、温度計、ディーンスターク装置および撹拌機をセットしたフラスコに、フェノール1128g(12.0mol)、サリチルアルデヒド122g(1.0mol)、パラトルエンスルホン酸12.5gを入れ、撹拌しながら45分間かけて120℃まで昇温した。反応により生じた縮合水をディーンスターク装置にて留去しながら120℃で3時間反応させた。反応終了後、49%水酸化ナトリウム水溶液5.1gを加えて中和し、脱水回路に切り替えて、3時間かけて180℃まで昇温した。傾注に水蒸気を吹き込みながら余剰のフェノールを一部除去し、軟化点108℃、水酸基当量98g/eqのフェノール樹脂中間体(1)280gを得た。
窒素導入管、冷却管、温度計、ディーンスターク装置および撹拌機をセットしたフラスコに、フェノール940g(10.0mol)、サリチルアルデヒド122g(1.0mol)、パラトルエンスルホン酸10.7g、トルエン1062gを入れ、撹拌しながら45分間かけて120℃まで昇温した。反応により生じた縮合水をディーンスターク装置にて留去しながら120℃で3時間反応させた。反応終了後、49%水酸化ナトリウム水溶液5.1gを加えて中和し、脱水回路に切り替えて、3時間かけて180℃まで昇温した。傾注に水蒸気を吹き込みながら余剰のフェノールを一部除去し、軟化点117℃、水酸基当量98g/eqのフェノール樹脂中間体(2)277gを得た。
フェノール樹脂中間体(1)98g(1.0mol)を、「TPM-113」に変更した以外は実施例1と同様にしてエポキシ樹脂(1’)を得た。エポキシ樹脂(1’)のGPCチャート図を図5に、HPLCチャート図を図6に示す。エポキシ樹脂(1’)のエポキシ当量は169g/eq、150℃での溶融粘度は1.0dPa・sであった。また、GPCチャート図から算出されるエポキシ樹脂(1’)中の3核体(X)の含有量は65.8%、HPLCチャート図から算出される3核体(X)中の[o,p,p]結合体(x1)の含有量は20.2%、[o,o,p]結合体(x2)の含有量は52.1%[o,o,o]結合体(x3)の含有量は27.7%であった。その結果を表1に示す。
下記要領で硬化性樹脂組成物を配合し、それらの硬化物について各種評価を行った。配合量及び各種評価試験の結果を表2~4に示す。なお、表中の各成分の詳細は以下の通りである。
エポキシ樹脂(1) :実施例1で製造されたエポキシ樹脂
エポキシ樹脂(2) :実施例2で製造されたエポキシ樹脂
エポキシ樹脂(1’):比較製造例1で製造されたエポキシ樹脂
酸無水物硬化剤 :メチルテトラヒドロフタル酸無水物(DIC株式会社製「EP
ICLON B-570H」酸無水物基当量166g/eq)
1,2-DMZ :1,2-ジメチルイミダゾール
ジシアンジアミド :三菱化学株式会社製「JERキュアDICY-7」
DCMU :N,N-ジメチル-N’-(3,4-ジクロロフェニル)尿素
(保土ヶ谷化学工業株式会社製「DCMU」)
4,4’-ジアミノジフェニルスルホン
:和歌山精化工業株式会社製「SEIKACURE-S」
下記表2~4に示す割合で各成分を配合し、溶融混練により均一混合して実施例3~比較例3の硬化性樹脂組成物を得た。
実施例3~4、比較例1で得られた硬化性樹脂組成物を幅90mm、長さ110mm、高さ2mmの型枠内に流し込み、150℃で1時間プレス成形し硬化物を得た。これをダイヤモンドカッターにて幅5mm、長さ50mmに切り出し、エスアイアイ・ナノテクノロジー社製「DMS6100」を用いて以下の条件による両持ち曲げによる動的粘弾性を測定した。貯蔵弾性率(E’)のオンセット温度をガラス転移温度(Tg)として評価した。その結果を表2に示す。
[測定条件]
測定温度範囲:室温~260℃
昇温速度:3℃/分
周波数:1Hz(正弦波)
歪振幅:10μm
実施例5~8、比較例2~3で得られた硬化性樹脂組成物を幅90mm、長さ110mm、高さ2mmの型枠内に流し込み、150℃で1時間プレス成形し硬化物を得た。これをダイヤモンドカッターにて幅5mm、長さ50mmに切り出し、エスアイアイ・ナノテクノロジー社製「DMS6100」を用いて以下の条件による両持ち曲げによる動的粘弾性を測定した。tanδが最大値となる温度をガラス転移温度(Tg)として評価した。その結果を表3、4に示す。
[測定条件]
測定温度範囲:室温~260℃
昇温速度:3℃/分
周波数:1Hz(正弦波)
歪振幅:10μm
実施例3~6、比較例1~2で得られた硬化性樹脂組成物を幅90mm、長さ110mm、高さ2mmの型枠内に流し込み、150℃で1時間プレス成形し硬化物を得た。JIS K6911に準拠して、硬化物の曲げ強度及び曲げ弾性率を測定した。その結果を表2、3に示す。
実施例7~8、比較例3で得られた硬化性樹脂組成物を幅90mm、長さ110mm、高さ2mmの型枠内に流し込み、150℃で1時間プレス成形したのち、さらに3時間加熱して硬化物(試験片2)を得た。得られた試験片2の曲げ強度及び曲げ弾性率を、JIS K6911に準拠して測定した。その結果を表4に示す。
実施例3~8、比較例2~3で得られた硬化性樹脂組成物から得られた前記硬化物を温度121℃、湿度100%の環境下に6時間静置した後、先と同様の方法でガラス転移温度、曲げ強度及び曲げ弾性率を測定した。さらに、湿熱試験前の値に対する湿熱試験後の値を計算し、物性保持率として評価した。その結果を表3~4に示す。
Claims (15)
- 樹脂中の前記3核体(X)の含有量が、GPC測定における面積比率で70%以上である請求項1記載のエポキシ樹脂。
- エポキシ当量が160~170g/当量である請求項1記載のエポキシ樹脂。
- 前記ヒドロキシベンズアルデヒドが、オルソヒドロキシベンズアルデヒドである請求項1記載のエポキシ樹脂。
- フェノールとオルソヒドロキシベンズアルデヒドとを、両者のモル比[(フェノール):(ヒドロキシベンズアルデヒド)]が1:0.05~1:0.25となる割合で反応させて得られるフェノール樹脂中間体得、次いで、得られたフェノール樹脂中間体とエピクロルヒドリンとを反応させて得られる請求項5のエポキシ樹脂。
- フェノールとオルソヒドロキシベンズアルデヒドとを、両者のモル比[(フェノール):(ヒドロキシベンズアルデヒド)]が1:0.05~1:0.25となる割合で反応させてフェノール樹脂中間体得、次いで、得られたフェノール樹脂中間体とエピクロルヒドリンとを反応させることを特徴とするエポキシ樹脂の製造方法。
- 150℃での溶融粘度が1mPa・s~100mPa・sの範囲である請求項1記載のエポキシ樹脂。
- 請求項1記載のエポキシ樹脂と、硬化剤とを含有する硬化性樹脂組成物。
- 前記硬化剤が、酸無水物、ジシアンジアミド化合物又は芳香族アミン化合物のいずれかである請求項10記載の硬化性樹脂組成物。
- 請求項10記載の硬化性樹脂組成物を硬化させてなる硬化物。
- 請求項1記載のエポキシ樹脂と、硬化剤と、強化繊維とを含有する繊維強化複合材料。
- 前記硬化剤が、酸無水物、ジシアンジアミド化合物又は芳香族アミン化合物のいずれかである請求項13記載の繊維強化複合材料。
- 請求項13記載の繊維強化複合材料を硬化させてなる成形品。
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